HARDMASK COMPOSITION, METHOD OF FORMING PATTERN USING THE HARDMASK COMPOSITION, AND HARDMASK FORMED FROM THE HARDMASK COMPOSITION

Description

FIELD OF THE INVENTION

[0001] The present disclosure relates to a hardmask composition, a method of forming a pattern, and a hardmask formed from the hardmask composition.

BACKGROUND OF THE INVENTION

[0002] The semiconductor industry has developed an ultrafine technique for providing a pattern having a size of several to several tens of nanometers. Such an ultrafine technique benefits from effective lithographic techniques. A typical lithographic technique includes providing a material layer on a semiconductor substrate, coating a photoresist layer on the material layer, exposing and developing the same to provide a photoresist pattern, and etching the material layer using the photoresist pattern as a mask.

[0003] In order to minimize or reduce the pattern to be formed, it may be difficult to provide a fine pattern having a desirable profile by only using the typical lithographic technique described above. Accordingly, a layer, called "a hardmask", may be formed between the material layer for etching and the photoresist layer to provide a fine pattern. The hardmask serves as an interlayer that transfers the fine pattern of the photoresist to the material layer through a selective etching process. Thus, the hardmask layer needs to have chemical resistance, thermal resistance, and etching resistance, so that it may tolerate various types of etching processes.

[0004] As semiconductor devices have become highly integrated, a height of a material layer has been maintained the same or has increased, but a line-width of the material layer has gradually narrowed. Thus, an aspect ratio of the material layer has increased. Because an etching process needs to be performed under such conditions, the heights of a photoresist layer and a hardmask pattern also need to be increased. However, there is a limit to the extent to which the heights of a photoresist layer and a hardmask pattern may be increased. In addition, the hardmask pattern may be damaged during the etching process for obtaining a material layer with a narrow line-width, and thus electrical characteristics of the devices may deteriorate.

[0005] In this regard, methods have been proposed which use a single layer or multiple layers, in which a plurality of layers of a conductive or insulating material are stacked, e.g., a polysilicon layer, a tungsten layer, and a nitride layer, as a hardmask. However, the single layer or the multiple layers require a relatively high deposition temperature, and thus physical properties of the material layer may be modified. Therefore, a novel hardmask material is needed.

[0006] EP 2 950 334 discloses a hardmask composition including a solvent and a 2-dimensional carbon nanostructure containing about 0.01 atom% to about 40 atom% of oxygen or a 2-dimensional carbon nanostructure precursor thereof.

SUMMARY OF THE INVENTION

[0007] Provided is a hardmask composition with improved etching resistance.

[0008] Provided is a method of forming a pattern using the hardmask composition.

[0009] Provided is a hardmask formed from the hardmask composition.

[0010] Additional aspects will be set forth in part in the description which follows and, in part, will be apparent from the description, or may be learned by practice of the presented embodiments.

[0011] According to some example embodiments, a hardmask composition includes a solvent and at least one of a derivative mixture and a composite. The derivative mixture may include a derivative of a two-dimensional (2D) carbon nanostructure and a derivative of a zero-dimensional (0D) carbon nanostructure. The composite may include a 2D carbon nanostructure and a 0D carbon nanostructure.

[0012] According to some example embodiments, a method of forming a pattern includes: forming an etching layer on a substrate; forming a hardmask on the etching layer, the forming the hardmask including providing the hardmask composition on the etching layer, wherein the hardmask includes a composite containing a 2D carbon nanostructure and a 0D carbon nanostructure; forming a photoresist layer on the hardmask; forming a hardmask pattern, the forming the hardmask pattern including etching the composite using the photoresist layer as an etching mask; and etching the etching layer using the hardmask pattern as an etching mask.

[0013] According to some example embodiments, a hardmask includes a composite containing a 2D carbon nanostructure and a 0D carbon nanostructure.

[0014] According to some example embodiments, a hardmask composition includes at least one of a two-dimensional (2D) carbon nanostructure and a derivative of the 2D carbon nanostructure. The hardmask composition further includes at least one of a zero-dimensional (0D) carbon nanostructure and a derivative of the 0D carbon nanostructure.

BRIEF DESCRIPTION OF THE DRAWINGS

[0015] These and/or other aspects will become apparent and more readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings in which:

FIG. 1 is a schematic diagram that illustrates a structure of a composite, according to one or more example embodiments, that may be used as a hardmask and includes a two-dimensional (2D) carbon nanostructure and a zero-dimensional (0D) carbon nanostructure;

FIGS. 2A to 2E illustrate a method of forming a pattern using a hardmask composition according to one or more example embodiments;

FIG. 2F illustrates a part of a method of forming a pattern using a hardmask composition according to one or more example embodiments;

FIGS. 3A to 3D illustrate a method of forming a pattern using a hardmask composition according to one or more example embodiments;

FIGS. 4A to 4D illustrate a method of forming a pattern using a hardmask composition according to one or more example embodiments; FIGS. 5A to 5D illustrate a method of forming a pattern using a hardmask composition according to one or more example embodiments.

FIGS. 6A and 6B respectively show Fourier transform (FT) transmission electron microscope (TEM) images of a composite of Example 1 and a graphene nanoparticle (GNP) of Comparative Example 1; and

FIG. 7 shows a Raman spectroscopy spectrum for OH-functionalized fullerene (C60) prepared in Preparation Example 5;

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0016] Reference will now be made in detail to embodiments, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout. In this regard, the present embodiments may have different forms and should not be construed as being limited to the descriptions set forth herein. Accordingly, the embodiments are merely described below, by referring to the figures, to explain aspects. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

[0017] Hereinafter, a hardmask composition according to one or more example embodiments, a method of forming a pattern using the hardmask composition, and a hardmask formed from the hardmask composition will be described in detail.

[0018] A hardmask composition may include a solvent and i) a derivative mixture including a derivative of a two-dimensional (2D) carbon nanostructure and a derivative of a zero-dimensional (0D) carbon nanostructure; and/or ii) a composite including the 2D carbon nanostructure and the 0D carbon nanostructure. In other words, the hardmask composition may include the solvent and at least one of the derivative mixture and the composite.

[0019] The term "a derivative of a two-dimensional (2D) carbon nanostructure and a derivative of a zero-dimensional (0D) carbon nanostructure" denotes an analogous compound that is obtained by chemically modifying a two-dimensional (2D) carbon nanostructure and the zero-dimensional (0D) carbon nanostructure.

[0020] The 2D carbon nanostructure and the 0D carbon nanostructure may be classified according to the manner in which carbon atoms are connected. The definitions thereof are as follows.

[0021] The term "2D carbon nanostructure" as used herein refers to a sheet structure of a single atomic layer formed by a carbon nanostructure that forms polycyclic aromatic molecules in which a plurality of carbon atoms are covalently bound and aligned into a planar shape; a network structure in which a plurality of carbon structures each having a plate shape as a small film piece are interconnected and aligned into a planar shape; or a combination thereof. The covalently bound carbon atoms form repeating units that include 6-membered rings, but may also form 5-membered rings and/or 7-membered rings. The 2D carbon nanostructure may be formed by stacking a plurality of layers including several sheet structures and/or network structures, and an average thickness of the 2D carbon nanostructure may be 100 nanometers (nm) or less, for example, 10 nm or less, or in a range of 0.01 nm to 10 nm.

[0022] The 2D carbon nanostructure may be a graphene nanoparticle (GNP) having a size in a range of 1 nm to 10 nm, for example, 5 nm to 8 nm, and the number of layers of the GNP is 300 or less.

[0023] The 2D carbon nanostructure may have a 2D sheet form, a ratio of size to thickness thereof may be in a range of 3 to 30, for example, 5 to 25. When the 2D carbon nanostructure has a plate-like shape, the term "size" denotes a longitudinal length of the 2-dimensional flat shape. When the 2D carbon nanostructure has an oval shape, the term "size" may denote a major axis diameter.

[0024] For example, the 2D carbon nanostructure may be at least one of graphene, graphene quantum dots, reduced graphene oxide, and a heteroatom derivative thereof.

[0025] The term "0D carbon nanostructure" as used herein may include, for example, fullerenes (C20, C26, C28, C36, C50, C60, C70, and C2n, where n=12, 13, 14, or 100), boron buckyballs (B80, B90, and B92), a carborane (C₂B₁₀H₁₂), and a derivative thereof. A particle size of the 0D carbon nanostructure may be in a range of 0.6 nm to 2 nm.

[0026] The 0D carbon nanostructure may be, for example, fullerene having a particle size of 1 nm or less, for example, 0.7 nm to 1 nm; and a density in a range of 1.5 grams per cubic centimeter (g/cm³) to 1.8 g/cm³, for example, 1.7 g/cm³. All fullerenes have sp² carbon.

[0027] The number of carbon atoms of the 0D carbon nanostructure may be 26 or greater, for example, 60 or greater, for example, 60, 70, 76, 78, 80, 82, or 84.

[0028] The term "heteroatom derivative" as used herein refers to a derivative that contains a heteroatom, e.g., boron (B) or nitrogen (N).

[0029] The 2D carbon nanostructure may be, for example, at least one of graphene, graphene quantum dots, graphene nanoparticles, reduced graphene oxide, and a heteroatom derivative thereof.

[0030] The 2D carbon nanostructure may have, for example, a 2D sheet form, a ratio of size to thickness thereof may be in a range of 3 to 30.

[0031] The term "derivative of a 2D carbon nanostructure" as used herein refers to a precursor of a 2D carbon nanostructure or a 2D carbon nanostructure having a reactive functional group. The term "derivative of a 0D carbon nanostructure" as used herein refers to a precursor of a 0D carbon nanostructure or a 0D carbon nanostructure having a reactive functional group. For example, when a 0D carbon nanostructure is fullerene, a derivative of the 0D carbon nanostructure may be a start material for fullerene, or fullerene having a reactive functional group such as OH-functionalized fullerene. When a 2D carbon nanostructure is a GNP, a derivative of the 2D carbon nanostructure refers to a GNP having a reactive functional group such as a COOH-functionalized GNP, or a start material for a GNP.

[0032] A COOH-functionalized GNP may be obtained by adding chloroacetic acid to a bare GNP or a OH functionalized GNP.

[0033] A OH-functionalized GNP may be obtained by a known method of introducing a hydroxyl group to a GNP. For example, the OH-functionalized fullerene may be obtained by grinding fullerene to a predetermined or given size followed by addition of a base and a oxidizing agent and grinding the mixture. Examples of the base include sodium hydroxide. Examples of the oxidizing agent include hydrogen peroxide.

[0034] The composite may be a structure in which a 2D carbon nanostructure is bound to a 0D carbon nanostructure via a linker; or a laminate of the 2D carbon nanostructure and the 0D carbon nanostructure.

[0035] The composite may be a molecular composite, a covalent bonded structure, or a laminate.

[0036] The term "laminate of the 2D carbon nanostructure and the 0D carbon nanostructure" as used herein refers to a structure in which the 2D carbon nanostructure and the 0D carbon nanostructure are stacked. The term "molecular composite" as used herein refers to a composite form in which elements thereof are well-mixed in molecular unit such as a single compound.

[0037] A hardmask may include the composite containing the 2D carbon nanostructure and the 0D carbon nanostructure. Because the composite has improved density relative to a 2D carbon nanostructure such as a GNP, the hardmask including the composite may have improved etching resistance relative to a hardmask including a GNP only.

[0038] A mixture ratio of the 2D carbon nanostructure to the 0D carbon nanostructure in the composite may be in a range of 1:1 to 99:1, for example, 50:50 to 90:10, for example, 3:1 to 5:1. When the mixture ratio of the 2D carbon nanostructure to the 0D carbon nanostructure in the composite is within any of these ranges, a hardmask composition may have a desirable solubility, and when this hardmask composition is used, a hardmask having improved film uniformity and etching resistance may be prepared.

[0039] FIG. 1 is a schematic diagram that illustrates a structure of a composite, according to one or more example embodiments, that may be used as a hardmask and includes a 2D carbon nanostructure and a 0D carbon nanostructure. In FIG. 1, the 2D carbon nanostructure may be, for example, a GNP (having a particle size in a range of 7 nm to 8 nm), and the 0D carbon nanostructure may be, for example, fullerene, but example embodiments are not limited thereto.

[0040] Referring to FIG. 1, a composite 10 has a structure in which fullerene 12 is present between a plurality of 2D carbon nanostructures, e.g., GNPs, as a complex. The GNPs 11 and the fullerene 12 may form covalent bonds through a coupling reaction and be bound to each other via these covalent bonds. The composite 10 having such a structure may have an excellent density in a range of 1.6 g/cm³ to 1.8 g/cm³ because the fullerene 12 complements micropores of the GNPs 11. In addition, excellent solubility of the GNPs 11 and etching resistance of the fullerene 12 may exhibit a synergistic effect, and thus, a hardmask prepared using the composite may have improved etching resistance.

[0041] In the composite 10, the 2D carbon nanostructure may be bound to the 0D carbon nanostructure by a linker. The linker may be derived from reactive functional groups included in the 2D carbon nanostructure and the 0D carbon nanostructure. For example, the 2D carbon nanostructure may include a first reactive functional group and the 0D carbon nanostructure may include a second reactive functional group, which may be the same as or different than the first reactive functional group.

[0042] The reactive functional group (e.g., first reactive functional group and/or second reactive functional group) may be any suitable functional group that enables a coupling reaction between the 2D carbon nanostructure and the 0D carbon nanostructure. Examples of the reactive functional group (e.g., first reactive functional group and/or second reactive functional group) may include at least one of a halogen atom, a hydroxyl group, an alkoxy group, a cyano group, an amino group, an azide group, a carboxamidine group, a hydrazino group, a hydrazono group. a a carbamoyl group, a thiol group, an ester group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, and a phosphoric acid group or a salt thereof.

[0043] The linker may be one of an ester group (-C(=O)O-), an ether group (-O-), a thioether group (-S-), a carbonyl group ((-C)=O)-), an amide group (-C(=O)NH-), an imide group, and an organic group derived therefrom.

[0044] The composite may be a product of a reaction between the 2D carbon nanostructure having a reactive functional group and the 0D carbon nanostructure having a reactive functional group.

[0045] According to analysis of the fullerene by Raman spectroscopy, a maximum absorption peak may be observed at a Raman shift of 1,455 centimeters^-1 (cm^-1) to 1,500 cm^-1. This peak corresponds to a pentagonal pinch mode, which indicates that fullerene is included in the composite.

[0046] The composite may be, for example, a composite represented by Formula 1, a composite represented by Formula 2, or a composite represented by Formula 3:

wherein, in Formula 1, A indicates fullerene, B indicates graphene and a linker is -O-C(=O)-O-,

[0047] The composite represented by Formula 1 may be a product of a reaction between graphene to which a hydroxyl group is bound and fullerene to which a carboxyl group is bound,

wherein in Formula 2, R indicates a group represented by Formula 2a:



wherein, in Formula 3, n may be an integer from 1 to 10, for example, 1.

[0048] The GNP used as a 2D carbon nanostructure may have a 2D plate-like shape or a spherical shape. For example, the GNP may have a spherical shape. Here, the term "spherical" denotes all types of shape that is substantially close to a sphere. For example, the spherical shape may be a spherical shape or an oval shape.

[0049] When the GNP has a spherical shape, the term "size" denotes an average particle diameter of the GNP. When the GNP has a plate-like shape, the term "size" denotes a longitudinal length of the 2-dimensional flat shape. When the GNP has an oval shape, the term "size" may denote a major axis length. A size of the GNP may be in a range of 1 nanometers (nm) to 10 nm, for example, 5 nm to 10 nm, or 7 nm to 8 nm. When a size of the GNP is within any of these ranges, an amount of the edge carbon is greater than 20 atom% based on the total amount of carbon of the GNP, and thus an etching rate of a hardmask formed from the hardmask composition may be excessively high. Also, when a size of the GNP is within any of these ranges, an etching rate of the hardmask may be appropriately controlled, and dispersibility of the GNP in the hardmask composition may be improved.

[0050] The number of layers of the GNP may be 300 or less, for example, 100 or less, or in some embodiments, in a range of 1 to 20. Also, a thickness of the GNP may be 100 nm.

[0051] When a size, the number of layers, and a thickness of the GNP are within any of these ranges above, the hardmask composition may have improved stability.

[0052] The GNP contains an edge carbon (edge C) existing at an edge site and a center carbon (center C) existing at a center site. The edge carbon has an sp³ bonding structure, and the center carbon has an sp² bonding structure. Since a functional group (e.g., oxygen or nitrogen) may be bound to the edge carbon, reactivity of the edge carbon with respect to an etching solution may be greater than that of the center carbon.

[0053] In a GNP according to one or more example embodiments, an amount of the edge carbon may be about 20 atom% or less, for example, in a range of 1.2 atom% to 19.1 atom%.

[0054] In the GNP, an amount of the edge carbon and the center carbon may be calculated using a carbon-carbon bond length in the GNP.

[0055] An amount of oxygen contained in the GNP may be in a range of 0.01 atom% to 40 atom%. An amount of oxygen may be in a range of 6.5 atom% to 19.9 atom%, for example, 10.33 atom% to 14.28 atom%. The amount of oxygen may be measured using, for example, an X-ray photoelectron spectroscopy (XPS) analysis. When the amount of oxygen is within any of these ranges, degassing may not occur during an etching process of the hardmask formed from the hardmask composition, and the hardmask may have desirable etching resistance. When the amount of oxygen of the GNP is within any of these ranges, the GNP has hydrophilic property, and thus an adhesive strength of the GNP to another layer may improve. Also, solvent dispersibility of the GNP improves, and thus a hardmask composition may be more easily manufactured. In addition, etching resistance with respect to an etching gas may improve due to a high bond dissociation energy of the functional group including an oxygen atom.

[0056] Each of D50, D90, and D10 of the GNPs denotes a particle size when the GNPs are accumulated at a volume ratio of 50%, 90%, or 10%. Here, a particle size may refer to an average particle diameter when the GNPs have a spherical shape, or a longitudinal length when the GNPs do not have a spherical shape (e.g., have an oval or a rectangular shape).

[0057] In a hardmask according to one or more example embodiments, light scattering does not occur in a range of visible light, and a transmittance of the hardmask at a wavelength of 633 nm is 99% or higher. When a hardmask having improved transmittance as such is used, sensing of a hardmask pattern and an align mask for patterning an etching layer may become easier, and thus the etching layer may be patterned at a finer and more compact pattern size.

[0058] The GNPs contained in the hardmask may have k that is 0.5 or lower, for example, 0.3 or lower, or in some embodiments, 0.1 or lower, at a wavelength of 633 nm. For comparison, k of graphite is in a range of 1.3 to 1.5, and k of graphene, which is only formed of an sp² bond structure, is in a range of 1.1 to 1.3.

[0059] k is an extinction coefficient which is measured using a spectroscopic ellipsometer. When k of the GNPs is within the range above, and a hardmask formed using the GNPs is used, an align mark may be more easily sensed.

[0060] The total thickness of the GNP may be, for example, in a range of 0.34 nm to 100 nm. When GNPs have a thickness as such, the GNPs may have a stable structure. A GNP according to one or more example embodiments includes some oxygen atoms in addition to carbon atoms, rather than having a complete C=C/C-C conjugated structure. Also, a carboxyl group, a hydroxyl group, an epoxy group, or a carbonyl group may be present at the terminus of a 2-dimensional carbon nanostructure in the GNP.

[0061] The GNP may have improved solvent dispersibility, and thus manufacture of a hardmask composition with improved stability is convenient. Also, the GNP may improve etching resistance against an etching gas.

[0062] At least one functional group selected from a hydroxyl group, an epoxy group, a carboxyl group, a carbonyl group, an amine group, and an imide group may be bound at the terminus of the GNP. When the functional group is bound at the terminus of the GNP as described above, etching resistance of a hardmask formed from the hardmask composition may be better than that of a hardmask in which the functional group is present in the center of the GNP as well as at the terminus of the GNP.

[0063] An amount of the GNPs is in a range of about 0.1 percent by weight (wt%) to 40 wt%. When the amount of the graphene nanoparticles is within this range, the GNP may have improved stability and etching resistance.

[0064] The GNP according to one or more example embodiments may have peaks observed at 1,340 cm^-1 to 1,350 cm^-1, 1,580 cm^-1, and 2,700 cm^-1 in Raman spectroscopy analysis. These peaks provide information of a thickness, a crystallinity, and a charge doping status of the GNP. The peak observed at 1,580 cm^-1 is a "G mode" peak, which is generated by a vibration mode corresponding to stretching of a carbon-carbon bond. Energy of the "G mode" is determined by a density of excess charge doped in the carbon nanostructure. Also, the peak observed at 2,700 cm^-1 is a "2D mode" peak that is useful in the evaluation of a thickness of the GNP. The peak observed at 1,340 cm^-1 to 1,350 cm^-1 is a "D mode" peak, which appears when an sp² crystal structure has defects and is mainly observed when many defects are found around edges of a sample or in the sample per se. Also, a ratio of a D peak intensity to a G peak intensity (an D/G intensity ratio) provides information of a degree of disorder of crystals of the GNP.

[0065] An intensity ratio (I_D/I_G) of a D mode peak to a G mode peak obtained from Raman spectroscopy analysis of the GNPs is 2 or lower, for example, in a range of 0.001 to 2.0.

[0066] An intensity ratio (I_2D/I_G) of a 2D mode peak to a G mode peak obtained from Raman spectroscopy analysis of the GNPs is 0.01 or higher. For example, the intensity ratio (I_2D/I_G) is within a range of 0.01 to 1.0, or 0.05 to 0.5.

[0067] When the intensity ratio of a D mode peak to a G mode peak and the intensity ratio of a 2D mode peak to a G mode peak are within any of these ranges, the GNP may have a relatively high crystallinity and a relatively small defect, and thus a bonding energy increases so that a hardmask formed using the GNP may have desirable etching resistance.

[0068] X-ray diffraction analysis using CuKα is performed on the GNP, and as a result of the X-ray diffraction analysis, the GNP may include a 2D layered structure having a (002) crystal face peak. The (002) crystal face peak may be observed within a range of 20° to 27°.

[0069] An interlayer distance (d-spacing) of the GNP obtained from the X-ray diffraction analysis may be in a range of about 0.3 nm to about 0.7 nm, for example, about 0.334 nm to about 0.478 nm. When the interlayer distance (d-spacing) is within this range, the hardmask composition may have desirable etching resistance.

[0070] The GNP may be formed as a single layer of 2D nanocrystalline carbon, or formed by stacking multiple layers of 2D nanocrystalline carbon.

[0071] The GNP according to one or more example embodiments has a higher content of sp² carbon than that of sp³ carbon and a relatively high content of oxygen, as compared with a conventional amorphous carbon layer. An sp² carbon bond, e.g., a bond of an aromatic structure, has a higher bonding energy than that of an sp³ carbon bond.

[0072] The sp³ structure is a 3-dimensional (3D) bonding structure of diamond-like carbon in a tetrahedral shape. The sp² structure is a 2D bonding structure of graphite in which a carbon to hydrogen ratio (a C/H ratio) increases and thus may secure resistance to dry etching.

[0073] In the 2D carbon nanostructure, an sp² carbon fraction may be equal to or a multiple of an sp³ carbon fraction. For example, an sp² carbon fraction may be a multiple of an sp³ carbon fraction by 1.0 to 10, or by 1.88 to 3.42.

[0074] An amount of the sp² carbon atom bonding structure is 30 atom% or greater, for example, 39.7 atom% to 62.5 atom%, in the C1s XPS analysis. Due to the mixing ratio, bond breakage of the GNP may be difficult because carbon-carbon bond energy is relatively high. Thus, when a hardmask composition including the GNP is used, etching resistance characteristics during the etching process may improve. A bond strength between the hardmask and adjacent layers may also increase.

[0075] A hardmask obtained using conventional amorphous carbon mainly includes an sp²-centered carbon atom bonding structure and thus may have desirable etching resistance and relatively low transparency. Therefore, when the hardmasks are aligned, problems may occur, and particles may be generated during a deposition process, and thus a hardmask formed using a diamond-like carbon having an sp³-carbon atom bonding structure has been developed. However, the hardmask has relatively low etching resistance and thus has a limit in process application.

[0076] A k value of graphite is in a range of 1.3 to 1.5, and a k value of graphene having an sp² structure is in a range of 1.1 to 1.3. A GNP according to one or more example embodiments has a k value that is 1.0 or lower, for example, in a range of 0.1 to 0.5 at a predetermined or given wavelength. Thus the GNP has improved transparency. Thus, when a hardmask including the GNP is used, an align mark may be more easily sensed during formation of a pattern of an etching layer. Therefore, the pattern may be more finely and evenly formed, and the hardmask may have desirable etching resistance.

[0077] In a hardmask composition according to one or more example embodiments, any suitable solvent capable of dispersing a 2D carbon nanostructure and a 0D carbon nanostructure may be used. For example, the solvent may be at least one of water, an alcohol-based solvent, and an organic solvent.

[0078] Examples of the alcohol-based solvent include methanol, ethanol, and isopropanol. Examples of the organic solvent include N,N-dimethylformamide, N-methylpyrrolidone, dichloroethane, dichlorobenzene, dimethylsulfoxide, xylene, aniline, propylene glycol, propylene glycol diacetate, 3-methoxy1,2-propanediol, diethylene glycol, gamma-butyrolactone, acetylacetone, cyclohexanone, propylene glycol monomethyl ether acetate, γ-butyrolactone, dichloroethane, O-dichlorobenzene, nitromethane, tetrahydrofuran, nitromethane, dimethyl sulfoxide, nitrobenzene, butyl nitrite, methyl cellosolve, ethyl cellosolve, diethylether, diethylene glycol methyl ether, diethylene glycol ethyl ether, dipropylene glycol methyl ether, toluene, hexane, methylethylketone, methyl isobutyl ketone, hydroxymethylcellulose, and heptane.

[0079] An amount of the solvent may be in a range of 100 parts to 100,000 parts by weight based on 100 parts by weight of the total weight of the 2D carbon nanostructure and the 0D carbon nanostructure. When the amount of the solvent is within this range, the hardmask composition may have an appropriate viscosity and thus may more easily form a layer.

[0080] A hardmask composition according to one or more example embodiments may have improved stability.

[0081] The hardmask composition may further include a first material selected from a monomer containing an aromatic ring and a polymer containing a repeating unit including the monomer; a second material selected from one of a hexagonal boron nitride, a chalcogenide-based material, and their precursors; or a mixture of the first material and the second material.

[0082] The first material may not be combined with the second material, or the first material may be combined to the second material by a chemical bond. The first material and the second material combined by a chemical bond may form a composite structure. The first material and the second material having the aforementioned functional groups may be bound to each other through a chemical bond.

[0083] The chemical bond may be, for example, a covalent bond. The covalent bond may include at least one selected from an ester group (-C(=O)O-), an ether group (-O-), a thioether group (-S-), a carbonyl group ((-C)=O)-), and an amide group (-C(=O)NH-).

[0084] The first material and the second material may include at least one of a hydroxyl group, a carboxyl group, an amino group, -Si(R₁)(R₂)(R₃) (wherein each of R₁, R₂, and R₃ are independently one of hydrogen, a hydroxyl group, a C₁-C₃₀ alkyl group, a C₁-C₃₀ alkoxy group, a C₆-C₃₀ aryl group, a C₆-C₃₀ aryloxy group, or a halogen atom), a thiol group (-SH), -Cl, -C(=O)Cl, -SCH₃, a glycidyloxy group, a halogen atom, an isocyanate group, an aldehyde group, an epoxy group, an imino group, a urethane group, an ester group, an amide group, an imide group, an acryl group, a methacryl group, -(CH₂)_nCOOH (wherein n is an integer from 1 to 10), - CONH₂, a C₁-C₃₀ saturated organic group having a photosensitive functional group, and a C₁-C₃₀ unsaturated organic group having a photosensitive functional group.

[0085] The monomer containing an aromatic ring may be at least one of a monomer represented by Formula 4 and a monomer represented by Formula 5:

wherein, in Formula 4, R is a mono-substituted or a multi-substituted substituent that is at least one of a general photosensitive functional group, hydrogen, a halogen atom, a hydroxyl group, an isocyanate group, a glycidyloxy group, a carboxyl group, an aldehyde group, an amino group, a siloxane group, an epoxy group, an imino group, a urethane group, an ester group, an epoxy group, an amide group, an imide group, an acryl group, a methacryl group, a substituted or unsubstituted C₁-C₃₀ saturated organic group, and a substituted or unsubstituted C₁-C₃₀ unsaturated organic group.

[0086] The C₁-C₃₀ saturated organic group and the C₁-C₃₀ unsaturated organic group may have a photosensitive functional group. Examples of the photosensitive functional group include an epoxy group, an amide group, an imide group, a urethane group, and an aldehyde group.

[0087] Examples of the C₁-C₃₀ saturated organic group and the C₁-C₃₀ unsaturated organic group include a substituted or unsubstituted C₁-C₃₀ alkyl group, a substituted or unsubstituted C₁-C₃₀ alkoxy group, a substituted or unsubstituted C₂-C₃₀ alkenyl group, a substituted or unsubstituted C₂-C₃₀ alkynyl group, a substituted or unsubstituted C₆-C₃₀ aryl group, a substituted or unsubstituted C₆-C₃₀ aryloxy group, a substituted or unsubstituted C₂-C₃₀ heteroaryl group, a substituted or unsubstituted C₂-C₃₀ heteroaryloxy group, a substituted or unsubstituted C₄-C₃₀ carbocyclic group, a substituted or unsubstituted C₄-C₃₀ carbocyclic-oxy group, and a substituted or unsubstituted C₂-C₃₀ heterocyclic group.

[0088] In Formula 4, a binding site of R is not limited. Although only one R is shown in Formula 4 for convenience of description, R may be substituted at any site where substitution is possible.

        Formula 5     A-L-A'

wherein, in Formula 5, each of A and A' may be identical to or different from each other and may independently be a monovalent organic group derived from one of the monomers represented by Formula 4 and

[0089] L may be a linker which represents a single bond or is one of a substituted or unsubstituted C₁-C₃₀ alkylene group, a substituted or unsubstituted C₂-C₃₀ alkenylene group, a substituted or unsubstituted C₂-C₃₀ alkynylene group, a substituted or unsubstituted C₇-C₃₀ arylene-alkylene group, a substituted or unsubstituted C₆-C₃₀ arylene group, a substituted or unsubstituted C₂-C₃₀ heteroarylene group, a substituted or unsubstituted C₂-C₃₀ heteroarylene-alkylene group, a substituted or unsubstituted C₁-C₃₀ alkylene-oxy group, a substituted or unsubstituted C₇-C₃₀ arylene-alkylene-oxy group, a substituted or unsubstituted C₆-C₃₀ arylene-oxy group, a substituted or unsubstituted C₂-C₃₀ heteroarylene-oxy group, a substituted or unsubstituted C₃-C₃₀ heteroarylene-alkylene-oxy group, - C(=O)-, and -SO₂-.

[0090] In L, the substituted C₁-C₃₀ alkylene group, the substituted C₂-C₃₀ alkenylene group, the substituted C₂-C₃₀ alkynylene group, the substituted C₇-C₃₀ arylene-alkylene group, the substituted C₆-C₃₀ arylene group, the substituted C₂-C₃₀ heteroarylene group, the substituted C₃-C₃₀ heteroarylene-alkylene group, the substituted C₁-C₃₀ alkylene-oxy group, the substituted C₇-C₃₀ arylene-alkylene-oxy group, the substituted C₆-C₃₀ arylene-oxy group, the substituted C₂-C₃₀ heteroarylene-oxy group, and the substituted C₃-C₃₀ heteroarylene-alkylene-oxy group may be substituted with at least one substituent selected from a halogen atom, a hydroxyl group, an isocyanate group, a glycidyloxy group, a carboxyl group, an aldehyde group, an amino group, a siloxane group, an epoxy group, an imino group, a urethane group, an ester group, an epoxy group, an amide group, an imide group, an acryl group, and a methacryl group, or may be substituted with a photosensitive functional group.

[0091] The first material may be at least one of a compound represented by Formula 7 and a compound represented by Formula 8:

wherein, in Formula 7, R is the same as described with reference to Formula 4.

wherein, in Formula 8, R is the same as described with reference to Formula 4, and L is the same as described with reference to Formula 5.

[0092] In Formulae 7 and 8, a binding site of R is not limited. Although only one R is included in Formulae 7 and 8 for convenience of description, R may be substituted at any site where substitution is possible.

[0093] A weight average molecular weight of the polymer containing a repeating unit including a monomer containing an aromatic ring may be 300 to 30,000. When a polymer having a weight average molecular weight within this range is used, a thin film may be more easily formed, and a transparent hardmask may be manufactured.

[0094] In one or more example embodiments, the first material may be a compound represented by Formula 9:

wherein, in Formula 9, A may be a substituted or unsubstituted C₆-C₃₀ arylene group,

[0095] L may be a single bond or a substituted or unsubstituted C₁-C₆ alkylene group, and n may be an integer from 1 to 5.

[0096] The arylene group may be selected from groups of Group 1:

[0097] In some embodiments, the compound of Formula 9 may be represented by Formulae 9a to 9c:





wherein, in Formulae 9a, 9b, and 9c, each of L¹ to L⁴ may independently be a single bond or a substituted or unsubstituted C₁-C₆ alkylene group.

[0098] The first material may be selected from compounds represented by Formulae 9d to 9f:

[0099] The first material may be a copolymer represented by Formula 10:

[0100] R₁ may be a C₁-C₄ substituted or unsubstituted alkylene; R₂, R₃, R₇, and R₈ may each independently be hydrogen, a hydroxy group, a C₁-C₁₀ linear or branched cycloalkyl group, an C₁-C₁₀ alkoxy group, a C₆-C₃₀ aryl group, or a mixture thereof; R₄, R₅, and R₆ may each independently be hydrogen, a hydroxy group, a C₁-C₄ alkoxy group, an alkylphenylalkyleneoxy group, or a mixture thereof; and R₉ may be an alkylene group, an alkylenephenylenealkylene group, a hydroxyphenylalkylene group, or a mixture thereof, wherein x and y may each independently be a mole fraction of two repeating units in part A which is 0 to 1, where x+y=1; n may be an integer from 1 to 200; and m may be an integer from 1 to 200.

[0101] The first material may be represented by Formula 10a, 10b or 10c:

wherein, in Formula 10a, x may be 0.2, and y may be 0.8;

wherein, in Formula 10b, x may be 0.2, y may be 0.8, n=90, and m=10; and



wherein, in Formula 10c, x may be 0.2, y may be 0.8, n=90, and m=10.

[0102] The first material may be a copolymer represented by Formula 11 or 12:



wherein, in Formulae 11 and 12, m and n may each be an integer from 1 to 190, R₁ may be one of hydrogen (-H), a hydroxy group(-OH), a C₁-C₁₀ alkyl group, a C₆-C₁₀ aryl group, an allyl group, and a halogen atom, R₂ may be one of a group represented by Formula 9A, a phenyl group, a chrysene group, a pyrene group, a fluoroanthene group, an anthrone group, a benzophenone group, a thioxanthone group, an anthracene group, and their derivatives; R₃ may be a conjugated diene; and R₄ may be an unsaturated dienophile.

wherein, in Formulae 11 and 12, R₃ may be a 1,3-butadienyl group, or a 1,6-cyclopentadienylmethyl group, and R₄ may be a vinyl group or a cyclopentenylmethyl group.

[0103] The first material may be a polymer represented by one of Formulae 13 to 16.

wherein, in Formula 13, m+n=21, a weight average molecular weight thereof may be 0,000 g/mol, and a polydispersity thereof may be 2.1;

wherein, in Formula 14, a weight average molecular weight thereof may be 11,000 g/mol, and a polydispersity thereof may be 2.1;

wherein, in Formula 15, a weight average molecular weight thereof may be 10,000 g/mol, a polydispersity thereof may be 1.9, l+m+n=21, and n+m:l=2:1; and

wherein, in Formula 16, a weight average molecular weight thereof may be 10,000 g/mol, a polydispersity thereof may be 2.0, and n may be 20.

[0104] The GNP has a relatively low reactivity with respect to a C_xF_y gas, which is an etching gas used to perform etching on a material layer such as SiO₂ or SiN, and thus etching resistance of the GNP may increase. When an etching gas with a relatively low reactivity with respect to SiO₂ or SiN_x, such as SF₆ or XeF₆, is used, etching may be more easily performed on the GNP, and thus ashing may be more easily performed thereon as well. Moreover, the 2D layered nanostructure is a transparent material having a band gap, and thus the preparation process may be more easily carried out because an additional align mask may not be necessary.

[0105] The hexagonal boron nitride derivative is a hexagonal boron nitride (h-BN) or a hexagonal boron carbonitride (h-BxCyNz) (wherein the sum of x, y, and z may be 3). In the hexagonal boron nitride derivative, boron and nitrogen atoms may be regularly included in a hexagonal ring, or some of boron and nitrogen atoms may be substituted with carbon atoms while maintaining the hexagonal ring.

[0106] The metal chalcogenide-based material is a compound including at least one Group 16 (chalcogenide) element and at least one electropositive element. For example, the metal chalcogenide-based material may include one or more metal elements selected from molybdenum (Mo), tungsten (W), niobium (Nb), vanadium (V), tantalum (Ta), titanium (Ti), zirconium (Zr), hafnium (Hf), technetium (Tc), rhenium (Re), copper (Cu), gallium (Ga), indium (In), tin (Sn), germanium (Ge), and lead (Pb) and one chalcogen element selected from sulfur (S), selenium (Se), and tellurium (Te).

[0107] The metal chalcogenide-based material may be selected from molybdenum sulfide (MoS₂), molybdenum selenide (MoSe₂), molybdenum telluride (MoTe₂), tungsten sulfide (WS₂), tungsten selenide (WSe₂), and tungsten telluride (WTe₂). In some embodiments, the metal chalcogenide-based material may be molybdenum sulfide (MoS₂).

[0108] The hexagonal boron nitride has a flat hexagonal crystal structure, the vertices of which are occupied alternatively by boron and nitrogen atoms. A layered structure of the hexagonal boron nitride is a structure in which a boron atom and a nitrogen atom neighboring each other overlap due to their polarities, and this structure is also referred as "an AB stacking". The hexagonal boron nitride may have a layered structure in which nanolevel-thin sheets are stacked in layers, and these layers may be separated or detached from each other to form a single layer or multiple layers of a hexagonal boron nitride sheet.

[0109] The hexagonal boron nitride according to one or more example embodiments may have a peak observed at 1360 cm^-1 in Raman spectroscopy analysis.

[0110] This location of the peak may reveal the number of layers in the hexagonal boron nitride. Through atomic force microscopic (AFM) analysis, Raman spectroscopy analysis, and transmission electron microscope (TEM) analysis performed on the hexagonal boron nitride, it may be found that the hexagonal boron nitride has a nanosheet structure.

[0111] X-ray diffraction analysis using CuKα is performed on the hexagonal boron nitride, and as a result of the X-ray diffraction analysis, the hexagonal boron nitride may include a 2D layered structure having a (002) crystal face peak. The (002) crystal face peak may be observed within a range of 20° to 27°.

[0112] An interlayer distance (d-spacing) of the hexagonal boron nitride obtained from the X-ray diffraction analysis may be in a range of 0.3 nm to 0.7 nm, for example, 0.334 nm to 0.478 nm. An average particle diameter of the hexagonal boron nitride crystals obtained from the X-ray diffraction analysis may be 1 nm or greater, for example, in a range of 23.7 Angstroms (Å) to 43.9 Å. When the interlayer distance (d-spacing) is within this range, the hardmask composition may have desirable etching resistance.

[0113] The hexagonal boron nitride may be formed as a single layer of 2D boron nitride, or formed by stacking multiple layers of 2D boron nitride.

[0114] Hereinafter, a method of preparing a hardmask using the hardmask composition according to one or more example embodiments will further be described.

[0115] A hardmask composition according to one or more example embodiments may include a derivative mixture including a derivative of a 2D carbon nanostructure, a derivative of a 0D carbon nanostructure, and a solvent. In some embodiments, the hardmask composition may include a composite including a 2D carbon nanostructure and a 0D carbon nanostructure; and a solvent. When the hardmask composition includes a derivative of a 2D carbon nanostructure, a derivative of a 0D carbon nanostructure, and a solvent, a derivative mixture (or composite) including the derivative of the 2D carbon nanostructure and the derivative of the 0D carbon nanostructure may be formed in-situ when forming a pattern using the hardmask composition.

[0116] An etching layer may be coated with the hardmask composition and dried to form a hardmask.

[0117] Examples of the derivative of the 2D carbon nanostructure include a COOH-functionalized GNP and a GNP precursor. Examples of the derivative of the 0D carbon nanostructure include a OH-functionalized fullerene.

[0118] During or after the coating the etching layer with the hardmask composition, heat treatment may be performed on the hardmask composition. Conditions for the heat treatment may vary depending on a material for the etching layer, but a temperature of the heat treatment may be from room temperature (20°C to 25°C) to 1,500°C.

[0119] The heat treatment may be performed in an inert gas atmosphere or in vacuum.

[0120] A heating source of the heat treatment may be induction heating, radiant heat, lasers, infrared rays, microwaves, plasma, ultraviolet rays, or surface plasmon heating.

[0121] The inert gas atmosphere may be prepared by mixing a nitrogen gas and/or an argon gas.

[0122] After the heat treatment, the solvent may be removed. Subsequently, c-axis arrangement of graphene may be performed. The resultant from which the solvent is removed may be baked at a temperature of 400°C or lower, for example, 100°C to 400°C. Then, another heat treatment may be further performed on the baked resultant at a temperature of 800°C or lower, for example, in a range of 400°C to 800°C.

[0123] A thermal reduction process may proceed during the heat treatment. When the GNP undergoes the thermal reduction process, a content of oxygen in the GNP may decrease.

[0124] In some embodiments, the baking process may not be performed, and the heat treatment may only be performed.

[0125] When the temperatures of the heat treatment and the baking process are within any of these ranges, the prepared hardmask may have desirable etching resistance. A temperature increasing rate in the heat treatment and the baking process may be 1°C/min to 1,000°C/min. When a temperature increasing rate is within this range, the deposited layer may not be damaged due to a rapid temperature change, and thus process efficiency may be desirable.

[0126] A thickness of the hardmask may be in a range of 10 nm to 10,000 nm.

[0127] Hereinafter, a method of preparing a GNP that may be used as a 2D carbon nanostructure will further be described.

[0128] In a first preparation method, an interlayer insertion material may be intercalated into graphite to prepare a graphite intercalation compound (GIC), and a GNP may be obtained therefrom.

[0129] The interlayer insertion material may be, for example, potassium sodium tartrate. When potassium sodium tartrate is used as the interlayer insertion material, the material may intercalate into graphite without an additional surfactant or a solvent during a solvo-thermal reaction to prepare a GIC, and then desired GNPs may be obtained by selecting particles according to a particle size of the resultant. Potassium sodium tartrate may serve as an interlayer insertion material and as a solvent at the same time.

[0130] The solvo-thermal reaction may be performed in, for example, an autoclave. The solvo-thermal reaction may be performed at a temperature, for example, in a range of 25°C to 400°C, or in some embodiments, at 250°C.

[0131] Examples of graphite as a starting material include natural graphite, kish graphite, synthetic graphite, expandable graphite or expanded graphite, or a mixture thereof.

[0132] A third preparation method may be a method of preparing a GNP to which a functional group is attached. The functional group may be, for example, a hydroxyl group. A GNP to which a hydroxyl group is attached may be highly soluble in a solvent, and thus may be utilized in various applications.

[0133] A GNP to which a hydroxyl group is attached according to one or more example embodiments may be prepared as follows.

[0134] A hydrothermal fusion reaction may be performed on a polycyclic aromatic hydrocarbon under an alkali aqueous solution condition, which may result in a GNP having a single crystal.

[0135] A hydrothermal reaction under the alkali aqueous solution condition may be performed at a temperature in a range of 90°C to 200°C. In the hydrothermal reaction, when alkaline species, e.g., OH^-, are present, hydrogen removal, condensation, or graphitization, and edge functionalization may occur.

[0136] Examples of the polycyclic aromatic hydrocarbon may include a pyrene and a 1-nitropyrene.

[0137] Before performing the hydrothermal reaction, a nitration reaction may be performed on the polycyclic aromatic hydrocarbon. The nitration reaction may be performed using a hot nitrate salt or hot nitric acid (e.g., hot HNO₃).

[0138] During the hydrothermal reaction, an amine-based material, e.g., NH₃, NH₂NH₂, may be added. When such an amine-based material is added thereto, water-soluble OH^- and an amine-functionalized GNP may be obtained.

[0139] According to a second preparation method, a GNP may be obtained by acid-treating graphite. For example, an acid and an oxidizing agent may be added to graphite, heated and allowed to react, and cooled to room temperature (25°C) to obtain a mixture containing a GNP precursor. An oxidizing agent may be added to the mixture containing the precursor to undergo an oxidizing process, and the resultant may be worked up to prepare a desired GNP.

[0140] Examples of the acid include sulfuric acid, nitric acid, acetic acid, phosphoric acid, hydrofluoric acid, perchloric acid, trifluoroacetic acid, hydrochloric acid, m-chlorobenzoic acid, and a mixture thereof. Examples of the oxidizing agent include, potassium permanganate, potassium perchlorate, ammonium persulfate, and a mixture thereof. Examples of the acid and the oxidizing agent are as described above. An amount of the oxidizing agent may be in a range of 0.00001 parts to 30 parts by weight based on 100 parts by weight of graphite.

[0141] The reaction may proceed by adding the acid and the oxidizing agent to graphite and heating the resultant using, for example, microwave. The microwave may have an output in a range of 50 Watts (W) to 1,500 W and a frequency in a range of 2.45 gigahertz (GHz) to 60 GHz. Time for applying the microwave may vary depending on the frequency of the microwave, but the microwave may be applied for 10 minutes to 30 minutes.

[0142] The work-up process may include controlling the resultant underwent the oxidizing process to room temperature, adding deionized water to dilute the resultant, and adding a base thereto to neutralize the resultant.

[0143] The work-up process may also include a process of selecting particles from the resultant according to a particle size to obtain desired GNPs.

[0144] Hereinafter, a method of forming a pattern using a hardmask composition according to one or more example embodiments will be described by referring to FIGS. 2A to 2E.

[0145] Referring to FIG. 2A, an etching layer 11 may be formed on a substrate 10. A hardmask composition according to one or more example embodiments may be provided on the etching layer 11 to form a hardmask 12.

[0146] A process of providing the hardmask composition may include at one of spin coating, air spraying, electrospraying, dip coating, spray coating, doctor blade coating, and bar coating.

[0147] In some embodiments, the hardmask composition may be provided using a spin-on coating method. The hardmask composition may coat the substrate 10 at a thickness of, for example, in a range of 10 nm to 10,000 nm, and in some embodiments, 10 nm to 1,000 nm, but the thickness of the hard composition is not limited thereto.

[0148] The substrate 10 is not particularly limited. For example, the substrate 10 may be at least one selected from a Si substrate; a glass substrate; a GaN substrate; a silica substrate; a substrate including at least one selected from nickel (Ni), cobalt (Co), iron (Fe), platinum (Pt), palladium (Pd), gold (Au), aluminum (Al), chromium (Cr), copper (Cu), manganese (Mn), molybdenum (Mo), rhodium (Rh), iridium (Ir), tantalum (Ta), titanium (Ti), tungsten (W), uranium (U), vanadium (V), and zirconium (Zr); and a polymer substrate.

[0149] A photoresist layer 13 may be formed on the hardmask 12.

[0150] As shown in FIG. 2B, a photoresist pattern 13a may be formed by exposing and developing the photoresist layer 13 using a known method.

[0151] The process of exposing the photoresist layer 13 may be performed using, for example, ArF, KrF, or extreme ultra violet (EUV). After the exposing process, heat treatment may be performed on the exposed photoresist layer 13 at a temperature in a range of 200°C to 500°C.

[0152] In the developing process, a developing solution, e.g., an aqueous solution of tetramethylammonium hydroxide (TMAH), may be used.

[0153] Subsequently, the hardmask 12 may be etched using the photoresist pattern 13a as an etching mask to form a hardmask pattern 12a on the etching layer 11 (FIG. 2C).

[0154] A thickness of the hardmask pattern 12a may be in a range of 10 nm to 10,000 nm. When the thickness of the hardmask pattern 12a is within this range, the layer may have desirable etching resistance as well as desirable homogeneousness.

[0155] For example, the etching process may be performed using a dry etching method using an etching gas. Examples of the etching gas include at least one selected from CF₄, CHF₃, C₂F6, C₄F₈, CHF₃, Cl₂, and BCl₃.

[0156] In some embodiments, when a mixture gas of C₄F₈ and CHF₃ is used as an etching gas, C₄F₈ may be mixed with CHF₃ at a volume ratio in a range of 1:10 to 10:1.

[0157] The etching layer 11 may be formed as a plurality of patterns. The plurality of patterns may vary, for example, may be a metal pattern, a semiconductor pattern, and an insulator pattern. For example, the plurality of patterns may be various patterns applied to a semiconductor integrated circuit device.

[0158] The etching layer 11 may contain a material that is to be finally patterned. The material of the etching layer 11 may be, for example, a metal (e.g., aluminum or copper), a semiconductor (e.g., silicon), or an insulator (e.g., silicon oxide or silicon nitride). The etching layer 11 may be formed using various methods (e.g., sputtering, electronic beam deposition, chemical vapor deposition, and physical vapor deposition). For example, the etching layer 11 may be formed using a chemical vapor deposition method.

[0159] As shown in FIGS. 2D and 2E, the etching layer 11 may be etched using the hardmask pattern 12a as an etching mask to later form an etching layer pattern 11a having a desired fine pattern.

[0160] When the hardmask composition according to one or more example embodiments is used, a solution process may be available, coating equipment may not be necessary, ashing-off may be easily performed in an oxygen atmosphere, and mechanical properties may be excellent.

[0161] The hardmask according to one or more example embodiments may be a structure in which a 2D carbon nanostructure and a 0D carbon nanostructure are stacked.

[0162] The hardmask according to one or more example embodiments may be inserted between other layers so as to use the hardmask as a stopper in the manufacture of a semiconductor device.

[0163] FIG. 2F illustrates a part of a method of forming a pattern using a composition according to one or more example embodiments.

[0164] Referring to FIG. 2F, as previously-described with reference to FIG. 2A, an etching layer 11 may be formed on a substrate 10 and a hardmask 12 and a photoresist layer 13 may be formed on the etching layer 11. Then, as previously-described with reference to FIG. 2B, a photoresist pattern 13a may be formed on the hardmask 12. Thereafter, the hardmask 12 may be etched using the photoresist pattern 13a as an etching mask to form a hardmask pattern 12a on the etching layer 11. As shown in FIG. 2F, a portion of the photoresist pattern 13a may remain after the hardmask pattern 12a is formed.

[0165] Then, the etching layer 11 may be etched to form an etched layer pattern 11a having a desired fine pattern using a remaining portion of the photoresist pattern 13a and the hardmask pattern 12a as an etching mask. Afterwards, the hardmask pattern 12a and any residual portion of photoresist pattern 13a may be removed using O₂ ashing and/or wet stripping to form a structure including the etched layer pattern 11a on the substrate 10 (see FIG. 2E). For example, the wet stripping may be performed by using alcohol, acetone, or a mixture of nitric acid and sulfuric acid.

[0166] Hereinafter, a method of forming a pattern using a hardmask composition according to one or more example embodiments will be described by referring to FIGS. 3A to 3D.

[0167] Referring to FIG. 3A, an etching layer 21 may be formed on a substrate 20. The substrate 20 may be a silicon substrate, but is not limited thereto.

[0168] The etching layer 21 may be formed as, for example, a silicon oxide layer, a silicon nitride layer, a silicon nitroxide layer, a silicon carbide (SiC) layer, or a derivative layer thereof. Then, a hardmask composition according to one or more example embodiments may be provided on the etching layer 21 to form a hardmask 22.

[0169] An anti-reflection layer 30 may be formed on the hardmask 22. The anti-reflection layer 30 may include an inorganic anti-reflection layer, an organic anti-reflection layer, or a combination thereof. FIGS. 3A to 3C illustrate embodiments in which the anti-reflection layer 30 includes an inorganic anti-reflection layer 32 and an organic anti-reflection layer 34.

[0170] The inorganic anti-reflection layer 32 may be, for example, a SiON layer, and the organic anti-reflection layer 34 may be a polymer layer commonly used in the art having an appropriate refraction index and a relatively high absorption coefficient on a photoresist with respect to a wavelength of light.

[0171] A thickness of the anti-reflection layer 30 may be, for example, in a range of 100 nm to 500 nm.

[0172] A photoresist layer 23 may be formed on the anti-reflection layer 30.

[0173] A photoresist pattern 23a may be formed by exposing and developing the photoresist layer 23 using a known method. Subsequently, the anti-reflection layer 30 and the hardmask 22 may be sequentially etched using the photoresist pattern 23a as an etching mask to form an anti-reflection pattern 30a and a hardmask pattern 22a on the etching layer 21. The anti-reflection pattern 30a may include an inorganic anti-reflection pattern 32a and an organic anti-reflection pattern 34a.

[0174] FIG. 3B illustrates that the photoresist pattern 23a and an anti-reflection pattern 30a remain after forming the hardmask pattern 22a. However, in some cases, part of or the whole photoresist pattern 23a and the anti-reflection pattern 30a may be removed during an etching process for forming the hardmask pattern 22a.

[0175] In FIG. 3C, only the photoresist pattern 23a is removed.

[0176] The etching layer 21 may be etched using the hardmask pattern 22a as an etching mask to form a desired etching layer pattern 21a (see FIG. 3D).

[0177] As described above, the hardmask pattern 22a is removed after forming the etching layer pattern 21a. In the preparation of the hardmask pattern 22a according to one or more example embodiments, the hardmask pattern 22a may be more easily removed using a known method, and little residue may remain after removing the hardmask pattern 22a.

[0178] The removing process of the hardmask pattern 22a may be performed by, but not limited to, O₂ ashing and wet stripping. For example, the wet stripping may be performed using alcohol, acetone, or a mixture of nitric acid and sulfuric acid.

[0179] A GNP in the hardmask prepared as above may have an amount of sp² carbon structures higher than the amount of sp³ carbon structures. Thus, the hardmask may secure sufficient resistance to dry etching. In addition, such a hardmask may have desirable transparent properties, and thus an align mask for patterning may be more easily sensed.

[0180] FIGS. 4A to 4D illustrate a method of forming a pattern using a hardmask composition according to one or more example embodiments.Referring to FIG. 4A, an etching layer 61 may be formed on a substrate 60. Then, a hardmask 62 may be formed on the etching layer 61 and a first photoresist pattern 63a may be formed on the hardmask 62.

[0181] A material of the substrate 60 is not particularly limited, and the substrate 60 may be at least one of a Si substrate; a glass substrate; a GaN substrate; a silica substrate; a substrate including at least one of nickel (Ni), cobalt (Co), iron (Fe), platinum (Pt), palladium (Pd), gold (Au), aluminum (Al), chromium (Cr), copper (Cu), manganese (Mn), molybdenum (Mo), rhodium (Rh), iridium (Ir), tantalum (Ta), titanium (Ti), tungsten (W), uranium (U), vanadium (V), and zirconium (Zr); and a polymer substrate. The substrate 60 may be semiconductor-on-insulator (SOI) substrate such as a silicon-on-insulator substrate.

[0182] The etching layer 61 may be formed as, for example, a silicon oxide layer, a silicon nitride layer, a silicon nitroxide layer, a silicon oxynitride (SiON) layer, a silicon carbide (SiC) layer, or a derivative thereof. However, example embodiments are not limited thereto.

[0183] Thereafter, a hardmask composition according to one or more example embodiments may be provided on the etching layer 61 to form a hardmask 62.

[0184] Thereafter, as shown in FIG. 4B, a second photoresist pattern 63b may be formed on top of the hardmask 62. The first and second photoresist patterns 63a and 63b may be alternately arranged.

[0185] In FIG. 4C, the hardmask layer 62 may be etched using the first and second photoresist patterns 63a and 63b as an etch mask to form a hardmask pattern 62a. Then, in FIG. 4D, the etching layer 61 may be etched to form an etching layer pattern 61a.

[0186] Even though FIGS. 4C and 4D illustrate the first and second photoresist patterns 63a and 63b remain on top of the hardmask pattern 62a after forming the hardmask pattern 62a, example embodiments are not limited thereto. A portion and/or an entire portion of the first and second photoresist patterns 63a and 63b may be removed during (and/or after) the process of forming the hardmask pattern 62a and/or the etching layer pattern 61a in FIGS. 4C and 4D.

[0187] FIGS. 5A to 5D illustrate a method of forming a pattern using a hardmask composition according to one or more example embodiments.

[0188] Referring to FIG. 5A, as previously described with reference to FIG. 3A, a stacked structure including the substrate 20, etching layer 21, hardmask layer 22, anti-reflection layer 30, and photoresist layer 23 may be formed.

[0189] Thereafter, the photoresist layer may be exposed and developed to form a photoresist pattern 23a. The anti-reflection layer 30 may be etched by using the photoresist pattern 23a as an etching mask to form an anti-reflection layer pattern 30a on the etching layer 21. The anti-reflection layer pattern 30a may include an inorganic anti-reflection layer pattern 32a and an organic anti-reflection layer pattern 34a.

[0190] As shown in FIG. 5B, a dielectric layer 70 (e.g., silicon oxide) may be coated on the photoresist pattern 23a.

[0191] Referring to FIG. 5C, spacers 72 may be formed by etching the dielectric layer 70. A hardmask pattern 22b may be formed by etching the hard mask layer 22 using the photoresist pattern 23a and spacers 72 as an etch mask.

[0192] Referring to FIG. 5D, the photoresist pattern 23a and anti-reflection layer pattern 30a may be removed using the spacers 72 as an etch mask. Next, a second hardmask pattern 22c may be formed by etching the hardmask pattern 22b using the spacers as an etch mask.

[0193] Thereafter, the etching layer 21 may be etched to form a pattern corresponding to the second hardmask pattern 22c using the spacers 72 and the second hardmask pattern 22c as an etch mask. Additionally, the spacers 72 and second hardmask pattern 22c may be subsequently removed after patterning the etching layer 21.

[0194] According to one or more example embodiments, a pattern formed using a hardmask composition may be used in the manufacture and design of an integrated circuit device according to a preparation process of a semiconductor device. For example, the pattern may be used in the formation of a patterned material layer structure, e.g., metal lining, holes for contact or bias, insulation sections (for example, a Damascene Trench (DT) or shallow trench isolation (STI)), or a trench for a capacitor structure.

[0195] Hereinafter, one or more example embodiments will be described in detail with reference to the following examples. However, these examples are not intended to limit the scope of the one or more example embodiments.

[0196] Preparation Example 1: Preparation of graphene nanoparticle (GNP)

[0197] 20 milligrams (mg) of graphite (available from Aldrich Co., Ltd.) and 100 mg of potassium sodium tartrate were added to an autoclave vessel, and the mixture was allowed to react at a temperature of 250°C for 60 minutes.

[0198] Once the reaction was complete, the resultant was centrifuged using a filter (8,000 nominal molecular weight limit (NMWL) and 10,000 NMWL, Amicon Ultra-15) to select a particle size, and this underwent dialysis to remove residues. Then the resultant was dried to obtain a spherical GNP having a particle diameter of 10 nm.

Preparation Example 2: Preparation of GNP

[0199] 20 mg of graphite (available from Alfa Aesar Co.,Ltd.) was dissolved in 100 milliliters (mL) of concentrated sulfuric acid, and the mixture was sonicated for about 1 hour. 1 gram (g) of KMnO₄ was added thereto, and a temperature of the reaction mixture was adjusted to be 25°C or lower.

[0200] At atmospheric pressure, microwaves (power: 600 W) were applied to the resultant while refluxing the resultant for 10 minutes. The reaction mixture was cooled so that a temperature of the reaction mixture was 25°C, and then 700 mL of deionized water was added to the reaction mixture to dilute the reaction mixture. Next, a sodium hydroxide was added to the reaction mixture in an ice bath so that a pH of the reaction mixture was adjusted to 7.

[0201] The reaction mixture was filtered through a porous membrane having a pore diameter of 200 nm to separate and remove graphene having a large size. Residues was removed from the obtained filtrate by performing dialysis, and the resultant was dried to obtain a spherical GNP having an average particle diameter of 5 nm.

Preparation Example 3: Preparation of GNP to which hydroxyl group (OH) is bound

[0202] 160 ml of nitric acid was added to 2 g of pyrene, and the mixture was refluxed at a temperature of 80°C for 12 hours to obtain a reaction mixture containing 1,3,6-trinitropyrene. The reaction mixture was cooled to room temperature, and 1 L of deionized water were added thereto to dilute the reaction mixture. Subsequently, this mixture was filtered through a fine porous film having a pore diameter of 0.22 µm.

[0203] 1.0 g of 1,3,6-trinitropyrene obtained after the filtration was dispersed in 0.6 L of a 0.2 molar (M) NaOH aqueous solution, and ultrasonic waves (500 W, 40 kHz) were then applied thereto for about 2 hours to obtain a suspension. The obtained suspension was placed in an autoclave vessel and was allowed to react at a temperature of 200°C for 10 hours. The resultant was cooled to room temperature, and filtered through a fine porous film having a pore diameter of 0.22 µm to remove an insoluble carbon product. Dialysis was performed on the resultant thus obtained after the filtration for 2 hours to obtain a GNP to which an OH group was bound. The GNP having OH group had an average particle diameter of 15 nm.

[0204] The GNPs prepared in Preparation Examples 1 and 3 had a structure in which a functional group containing oxygen was positioned at an edge thereof. The GNP prepared in Preparation Example 2 had a structure in which a functional group containing oxygen was positioned at an edge and on a plane thereof by using microwaves during the preparation process.

Preparation Example 4: Preparation of COOH-functionalized GNP

[0205] Chloroacetic acid was added to the GNP to which an OH group is bound prepared in Preparation Example 3, followed by heat treatment at a temperature of 80°C for 60 minutes. After the heat-treatment, a coupling reaction was performed to obtain a COOH-functionalized GNP. The GNP having COOH group had an average particle diameter of 15 nm.

Preparation Example 5: Preparation of OH-functionalized fullerene (C60)

[0206] 0.1 g of fullerene (C60) was ground in mortar, and 1 g of sodium hydroxide and 1 g of hydrogen peroxide (H₂O₂) was added thereto to obtain a mixture. The mixture was ground for 10 minutes to obtain OH-functionalized fullerene (C60).

Example 1: Preparation of hardmask composition

[0207] The OH-functionalized fullerene (C60) (particle size: 0.7 nm) prepared in Preparation Example 5 and the COOH-functionalized GNP (particle size: 7 nm to 8 nm) prepared in Preparation Example 4 were mixed together. Dichlorobenzene was added thereto as a solvent, and the resulting mixture underwent heat treatment at a temperature of about 80°C to thereby prepare a hardmask composition including a composite containing the OH-functionalized fullerene (C60) prepared in Preparation Example 5 and the COOH-functionalized GNP prepared in Preparation Example 4. In the hardmask composition, the OH-functionalized fullerene (C60) prepared in Preparation Example 5 was mixed with the COOH-functionalized GNP prepared in Preparation Example 4 at a weight ratio of 2:8. An amount of dichlorobenzene was 10 mL for 1 g of the OH-functionalized fullerene (C60) prepared in Preparation Example 5.

Example 2: Preparation of hardmask composition

[0208] The OH-functionalized fullerene (C60) prepared in Preparation Example 5 was mixed with a GNP precursor, e.g., pyrene. Water and sodium hydroxide (NaOH) were added thereto to obtain a mixture. The mixture was heat-treated at a temperature of about 250°C for 5 hours to perform a hydrothermal reaction to obtain a hardmask composition. In the hardmask composition, the OH-functionalized fullerene (C60) prepared in Preparation Example 5 was mixed with the COOH-functionalized GNP prepared in Preparation Example 4 at a weight ratio of 2:8. In the hardmask composition, an amount of the water was 600 mL for 1 g of the OH-functionalized fullerene (C60) prepared in Preparation Example 5, and an amount of the sodium hydroxide was 12 g for 1 g of the OH-functionalized fullerene (C60) prepared in Preparation Example 5.

Example 3: Preparation of silicon substrate on which silicon oxide pattern was formed

[0209] The hardmask composition prepared in Example 1 was spin coated on a silicon substrate on which a silicon oxide had been formed. Subsequently, baking was performed thereof at a temperature of 400°C for 2 minutes, to form a hardmask having a thickness of 200 nm and including the composite containing fullerene and GNP. The fullerene was mixed with the GNP at a weight ratio of 2:8.

[0210] The hardmask was coated with an ArF photoresist at a thickness of about 1,700 (Angstroms) A and then pre-baked at a temperature of 110°C for 60 seconds. The resultant was then exposed to light using a light exposing instrument available from ASML (XT: 1400, NA 0.93) and post-baked at a temperature of 110°C for 60 seconds. Next, the photoresist was developed using an aqueous solution of 2.38 wt% tetramethylammonium hydroxide (TMAH) to form a photoresist pattern.

[0211] Dry etching was performed using the photoresist pattern as a mask, and a CF₄/CHF₃ mixture gas. The etching conditions included 2.67 Pa (20 mTorr) of a chamber pressure, 1,800 W of a RT power, a 4/10 volume ratio of C₄F₈/CHF₃, and an etching time of 120 seconds.

[0212] O₂ ashing and wet stripping were performed on a post hardmask and an organic material remaining after the dry etching to obtain a silicon substrate, on which a desired silicon oxide pattern was formed as a final pattern.

Example 4: Preparation of silicon substrate on which silicon oxide pattern was formed

[0213] A silicon substrate, on which a silicon oxide pattern was formed, prepared in the same manner as in Example 3, except that the hardmask composition prepared in Example 2 was used in place of the hardmask composition prepared in Example 1.

Examples 5 and 6: Preparation of hardmask composition

[0214] Hardmask compositions were prepared in the same manner as in Example 2, except that the OH-functionalized fullerene (C60) prepared in Preparation Example 5 was mixed with the COOH-functionalized GNP prepared in Preparation Example 4 at a weight ratio of about 1:3 and about 1:2, respectively in the hardmask composition.

Examples 7 and 8: Preparation of silicon substrate on which silicon oxide pattern was formed

[0215] Silicon substrates, on which a silicon oxide pattern was formed, were prepared in the same manner as in Example 4, except that the hardmask compositions prepared in Examples 5 and 6 were respectively used in place of the hardmask composition prepared in Example 1.

Comparative Example 1

[0216] 10 g of a graphite powder was added to 50 mL of sulfuric acid (H₂SO₄), and the mixture was stirred at a temperature of 80°C for 4 hours to 5 hours.

[0217] The stirred mixture was diluted with 1 L of deionized water and stirred for about 12 hours. Then, the resultant was filtered to obtain pre-treated graphite.

[0218] Phosphorus pentoxide (P₂O₅) was dissolved in 80 mL of water, 480 mL of sulfuric acid was added thereto, 4 g of the pre-treated graphite was added thereto, and 24 g of potassium permanganate (KMnO₄) was added thereto. The mixture was stirred and sonicated for about 1 hour, and 600 mL of water (H₂O) was added thereto. When 15 mL of hydrogen peroxide (H₂O₂) was added to the reaction mixture, color of the reaction mixture changed from purple to light yellow, and the mixture was sonicated while being stirred. The reaction mixture was filtered to remove non-oxidized remaining graphite. In order to remove manganese (Mn) from the filtrate, 200 mL of HCI, 200 mL of ethanol, and 200 mL of water were added to the filtrate, and the mixture was stirred. The mixture was centrifuged to obtain a 2D carbon nanostructure precursor.

[0219] 0.5 g of the 2D carbon nanostructure precursor thus obtained was dispersed in 1 L of water to obtain a hardmask composition. While spray coating a silicon substrate, on which a silicon oxide had been formed, with the hardmask composition, the substrate was heat-treated at a temperature of 200 °C. Subsequently, the resultant was baked at a temperature of 400°C for 1 hour, and vacuum heat-treated at a temperature of 600°C for 1 hour to prepare a hardmask having a thickness of 200 nm and containing a GNP.

Comparative Example 2

[0220] fullerene was mixed with dichlorobenzene as a solvent to obtain a hardmask composition. In the hardmask composition, an amount of the dichlorobenzene was 10 mL for 1 g of fullerene.

[0221] In this case, solubility of fullerene to the solvent was poor, and thus it was difficult to obtain a homogeneous hardmask composition. A hardmask containing fullerene was prepared in the same manner as in Comparative Example 1, except that the foregoing hardmask composition was used in place of the hardmask composition prepared in Example 1.

[0222] In Comparative Example 2, it was difficult to form a hardmask in film form because solubility of fullerene to the solvent was poor.

Comparative Example 3

[0223] Fullerene (C60), a GNP (particle size: 7 nm to 8 nm), and solvent were mixed together to obtain a hardmask composition. The fullerene was mixed with the GNP at a weight ratio of 2:8.

[0224] A hardmask was prepared in the same manner as in Comparative Example 1, except that the foregoing hardmask composition was used in place of the hardmask composition prepared in Comparative Example 1.

Evaluation Example 1: Etching resistance

[0225] Etching resistance was evaluated by measuring a thickness difference between before and after the dry etching on the hardmasks and the silicon oxide layers using the hardmasks prepared in Examples 3 and 4 and Comparative Examples 1 and 3 and calculating an etch rate and an etching selection ratio according to Equations 1 and 2. The results of etching resistance evaluation are shown in Table 1. In Equation 1, the thin film comprises only the hardmask.

Table 1

Example	Etch rate (nm/sec)	Etching selectivity ratios
Example 3	0.8	2.5
Example 4	0.8	2.5
Comparative Example 1	1.0	2
Comparative Example 3	1.0	2

[0226] Referring to Table 1, it was found that the hardmasks prepared in Examples 3 and 4 had low etch rates and high etching selectivity ratios, as compared with those of the hardmasks prepared in Comparative Examples 1 and 3. Accordingly, the hardmask compositions used in Examples 3 and 4 were found to have improved etching resistance, as compared with the hardmask compositions used in Comparative Examples 1 and 3.

Evaluation Example 2: Density

[0227] Film densities of the hardmasks prepared in Examples 3 and 4 and Comparative Examples 1 and 3 are shown in Table 2.

Table 2

Example	Film density (g/cm3)
Example 3	1.8
Example 4	1.8
Comparative Example 1	1.4
Comparative Example 3	1.4

Evaluation Example 3: TEM analysis

[0228] TEM analysis was performed on the composite of Example 1 containing the OH-functionalized fullerene (C60) prepared in Preparation Example 5 and the COOH-functionalized GNP prepared in Preparation Example 4 and the GNP prepared in Comparative Example 1. The TEM analysis was performed by using Osiris available from Tecnai Co.,Ltd..

[0229] FIGS. 6A and 6B respectively show Fourier transform (FT) TEM images of the composite of Example 1 and the GNP of Comparative Example 1.

[0230] As shown in FIGS. 6A and 6B, a crystalline ring pattern was observed in the composite of Example 1, whereas a crystalline ring pattern was not observed in the GNP of Comparative Example 1.

Evaluation Example 4: Raman spectrum analysis

[0231] Raman spectroscopy analysis was performed for the OH-functionalized fullerene (C60) prepared in Preparation Example 5. Raman spectroscopy analysis was performed by using RM-1000 Invia instrument (514 nm, Ar⁺ ion laser). The results of Raman spectroscopy analysis is shown in FIG. 7.

[0232] As shown in FIG. 7, the OH-functionalized fullerene (C60) prepared in Preparation Example 5 exhibited a maximum absorption peak observed at a Raman shift of 1,459 cm^-1. The maximum absorption peak at 1,459 cm^-1 has relevance to a pentagonal pinch mode. When a composite is included in a hardmask, the composite including fullerene having a maximum absorption peak as such, the hardmask may have excellent etching resistance.

Evaluation Example 5: Transmittance

[0233] Transmittances of the hardmasks prepared in Examples 3 and 4 and Comparative Examples 1 to 3were measured by light exposure at a wavelength of 633 nm.

[0234] As the result, it was found that transmittances of the hardmask patterns prepared in Examples 3 and 4 were improved 99% or higher relative to transmittances of the hardmask patterns prepared in Comparative Examples 1 to 3. When a hardmask having improved transmittance as such is used, sensing of a hardmask pattern and an align mask for patterning an etching layer may become easier, and thus the etching layer may be patterned at a finer and more compact pattern size.

Evaluation Example 6: Pattern shape analysis

[0235] Etching was performed using the hardmasks prepared in Examples 3, 4, 7, and 8 and Comparative Examples 1 to 3. Then, surfaces of silicon substrates on which a silicon oxide pattern had been formed were observed using field emission scanning electron microscope (FE-SEM). The results thereof are shown in Table 3.

Table 3

Example	Pattern shape of the hardmask after etching thereon	Pattern shape of the silicon oxide after etching thereon
Example 3	Vertical shape	Vertical shape
Example 4	Vertical shape	Vertical shape
Example 7	Vertical shape	Vertical shape
Example 8	Vertical shape	Vertical shape
Comparative Example 1	Arc shape	Tapered shape
Comparative Example 2	Arc shape	Tapered shape
Comparative Example 3	Arc shape	Tapered shape

[0236] As shown in Table 3, the pattern shapes of the silicon oxides formed using the hardmasks of Examples 3, 4, 7, and 8 were found to be vertical, whereas those formed using the hardmasks Comparative Examples 1 to 3 were not vertical.

[0237] As apparent from the foregoing description, a hardmask including a hardmask composition according to one or more example embodiments may have desirable stability, and improved etching resistance and mechanical strength relative to those of a polymer or an amorphous carbon generally used, and the hardmask may be more easily removed after an etching process. When the hardmask is used, a pattern may be finely and evenly formed, and efficiency of a semiconductor process may be improved relative to when the hardmask is not used.

[0238] It should be understood that embodiments described herein should be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features or aspects within each embodiment should typically be considered as available for other similar features or aspects in other embodiments.

[0239] While one or more example embodiments have been described with reference to the figures, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the scope as defined by the following claims.

Claims

1. A hardmask composition comprising:

a solvent; and at least one of

a derivative mixture including a derivative of a two-dimensional (2D) carbon nanostructure and a derivative of a zero-dimensional (0D) carbon nanostructure, or

a composite including a 2D carbon nanostructure and a 0D carbon nanostructure.

2. The hardmask composition of claim 1, wherein
the hardmask composition includes the composite,
the composite is a structure in which the 2D carbon nanostructure is bound to the 0D carbon nanostructure by a linker, or
the composite is a laminate of the 2D carbon nanostructure and the 0D carbon nanostructure;
preferably wherein
the linker is at least one of an ester group (-C(=O)O-), an ether group (-O-), a thioether group (-S-), a carbonyl group ((-C)=O)-), an amide group (-C(=O)NH-), and an imide group, or
the linker is an organic group derived from at least one of an ester group (-C(=O)O-), an ether group (-O-), a thioether group (-S-), a carbonyl group ((-C)=O)-), an amide group (-C(=O)NH-), and an imide group.

3. The hardmask composition of claim 1, wherein
the hardmask composition includes the composite,
the composite is a product of a reaction between the 0D carbon nanostructure including a first reactive functional group and the 2D carbon nanostructure including a second reactive functional group, and
the first reactive functional group and the second reactive functional group independently each include at least one of a halogen atom, a hydroxyl group, an alkoxy group, a cyano group, an amino group, an azide group, a carboxamidine group, a hydrazino group, a hydrazono group, a carbamoyl group, a thiol group, an ester group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, and a phosphoric acid group or a salt thereof.

4. The hardmask composition of any of claims 1-3, wherein
the 0D carbon nanostructure is at least one of a fullerene, a boron buckyball, a carborane, and a derivative thereof; and/or
wherein the 2D carbon nanostructure is at least one of graphene, graphene quantum dots, reduced graphene oxide, and a heteroatom derivative thereof; and/or
wherein a size of the 2D carbon nanostructure is in a range of 1 nanometer (nm) to 10 nm; and/or
wherein a content of carbon in the 2D carbon nanostructure is in a range of 75 percent by weight (wt%) to 95 wt%.

5. The hardmask composition of claim 1, wherein
the 2D carbon nanostructure is a graphene nanoparticle (GNP) having a size in a range of 1 nm to 10 nm, and a number of layers of the GNP is greater than 0 and less than or equal to 300; and/or
wherein the 0D carbon nanostructure is a fullerene or a derivative thereof, and a number of carbon atoms in the 0D carbon nanostructure is one of 60, 70, 76, 78, 82, 82, and 84;
preferably wherein, according to analysis of the fullerene by Raman spectroscopy, a maximum absorption peak is observed at a Raman shift of 1,455 centimeters^-1 (cm^-1) to 1,500 cm^-1.

6. The hardmask composition of claim 1, wherein
the 2D carbon nanostructure is a 2D sheet having a size to thickness ratio in a range of 3 to 30.

7. The hardmask composition of claim 1, wherein
the 2D carbon nanostructure is a GNP, and
an intensity ratio of a D mode peak to a G mode peak obtained from Raman spectroscopy analysis of the GNP is greater than 0 and less than or equal to 2, and an intensity ratio of a 2D mode peak to a G mode peak is 0.01 or greater;
preferably wherein an sp² carbon fraction of the GNP is equal to an sp³ carbon fraction thereof or equal to a multiple of an sp³ carbon fraction thereof.

8. The hardmask composition of any of claims 1-7, wherein
the 2D carbon nanostructure is mixed with the 0D carbon nanostructure at a ratio of 1:1 to 99:1.

9. The hardmask composition of claim 1, wherein
the hardmask composition includes at least one of a compound represented by Formula 2, a compound represented by Formula 3, and a product of a reaction between graphene to which a hydroxyl group is bound and a fullerene to which a carboxyl group is bound:

wherein, in Formula 2, R indicates a group represented by Formula 2a:





wherein, in Formula 3, n is an integer from 1 to 10.

10. The hardmask composition of any of claims 1-9, wherein the solvent is at least one of water, methanol, isopropanol, ethanol, N,N-dimethylformamide, N-methylpyrrolidone, dichloroethane, dichlorobenzene, dimethylsulfoxide, xylene, aniline, propylene glycol, propylene glycol diacetate, 3-methoxy1,2-propanediol, diethylene glycol, gamma-butyrolactone, acetylacetone, cyclohexanone, propylene glycol monomethyl ether acetate, o-dichlorobenzene, nitromethane, tetrahydrofuran, nitromethane, dimethyl sulfoxide, nitrobenzene, butyl nitrite, methyl cellosolve, ethyl cellosolve, diethylether, diethylene glycol methyl ether, diethylene glycol ethyl ether, dipropylene glycol methyl ether, toluene, hexane, methylethylketone, methyl isobutyl ketone, hydroxymethylcellulose, and heptane; and/or
the hardmask composition further comprises:

one of a first material, a second material, and a mixture of the first material and the second material, wherein

the first material includes one of a monomer containing an aromatic ring and a polymer including a repeating unit containing the monomer, and

the second material includes one of hexagonal boron nitride, a chalcogenide-based material, and a precursor thereof.

11. A method of forming a pattern, the method comprising:

forming an etching layer on a substrate,

forming a hardmask on the etching layer, the forming the hardmask including providing the hardmask composition of any of claims 1-10 on the etching layer, wherein the hardmask includes the composite of the 2D carbon nanostructure and the 0D carbon nanostructure,

forming a photoresist layer on the hardmask,

forming a hardmask pattern, the forming the hardmask pattern including etching the composite using the photoresist layer as an etching mask, and

etching the etching layer using the hardmask pattern as an etching mask;

preferably further comprising:
performing a heat treatment on the hardmask composition during or after the providing of the hardmask composition on the etching layer.

12. The method of claim 11, wherein a thickness of the hardmask is in a range of 10 nm to 10,000 nm; and/or
wherein the forming the hardmask includes using at least one of spin coating, air spraying, electrospraying, dip coating, spray coating, doctor blade coating, and bar coating during the providing the hardmask composition; and/or
wherein the forming the hardmask includes mixing the derivative of the 2D carbon nanostructure, the derivative of the 0D carbon nanostructure, and the solvent; and/or
wherein the derivative of the 2D carbon nanostructure is at least one of a COOH-functionalized GNP and a GNP precursor, and
the derivative of the 0D carbon nanostructure is an OH-functionalized fullerene; and/or
wherein the forming the hardmask includes
mixing the solvent and the composite including the 2D carbon nanostructure and the 0D carbon nanostructure, or

mixing the solvent, the derivative of the 2D carbon nanostructure, and the derivative of the 0D carbon nanostructure; or

wherein

the forming the hardmask pattern includes forming a laminate structure, and
the laminate structure includes the 2D carbon nanostructure and the 0D carbon nanostructure.

13. A hardmask comprising:

a composite including a 2D carbon nanostructure and a 0D carbon nanostructure;

preferably wherein

the hardmask includes a laminate structure, and

the laminate structure includes the 2D carbon nanostructure and the 0D carbon nanostructure.

14. A hardmask composition comprising:

at least one of a two-dimensional (2D) carbon nanostructure and a derivative of the 2D carbon nanostructure; and

at least one of a zero-dimensional (0D) carbon nanostructure and a derivative of the 0D carbon nanostructure.

15. The hardmask composition of claim 14, wherein
the hardmask composition includes the 0D carbon nanostructure, and
the 0D carbon nanostructure is at least one of a fullerene, a boron buckyball, a carborane, and a derivative thereof; or
wherein
the hardmask composition includes the 2D carbon nanostructure, and
the 2D carbon nanostructure is at least one of graphene, a graphene nanoparticle (GNP), graphene quantum dots, reduced graphene oxide, and a heteroatom derivative thereof; or
wherein
the at least one of the 2D carbon nanostructure and the derivative of the 2D carbon nanostructure is the 2D carbon nanostructure,
the at least one of the 0D carbon nanostructure and the derivative of the 0D carbon nanostructure is the 0D carbon nanostructure, and
the 2D carbon nanostructure and the 0D carbon nanostructure are connected to each other by a linker functional group.

Ansprüche

1. Hartmaskenzusammensetzung, umfassend:
ein Lösungsmittel und mindestens eines von

einem Derivatgemisch, enthaltend ein Derivat einer zweidimensionalen-(2D)-Kohlenstoffnanostruktur und ein Derivat einer nulldimensionalen-(OD)-Kohlenstoffnanostruktur oder

einen Verbundstoff, enthaltend eine 2D-Kohlenstoffnanostruktur und eine 0D-Kohlenstoffnanostruktur.

2. Hartmaskenzusammensetzung nach Anspruch 1, wobei
die Hartmaskenzusammensetzung den Verbundstoff enthält,

der Verbundstoff eine Struktur ist, in der die 2D-Kohlenstoffnanostruktur durch einen Verknüpfer mit der 0D-Kohlenstoffnanostruktur verbunden ist, oder

der Verbundstoff ein Laminat aus der 2D-Kohlenstoffnanostruktur und der 0D-Kohlenstoffnanostruktur ist;

vorzugsweise wobei

der Verknüpfer mindestens eines einer Estergruppe (-C(=O)O-), einer Ethergruppe (-O-), einer Thioethergruppe (-S-), einer Carbonylgruppe ((-C)=O)-), einer Amidgruppe (-C(=O)NH-) und einer Imidgruppe ist, oder

der Verknüpfer eine organische Gruppe ist, die von einer Estergruppe (-C(=O)O-), einer Ethergruppe (-O-),einer Thioethergruppe (-S-), einer Carbonylgruppe ((-C)=O)-), einer Amidgruppe (-C(=O)NH-) und einer Imidgruppe deriviert ist.

3. Hartmaskenzusammensetzung nach Anspruch 1, wobei
die Hartmaskenzusammensetzung den Verbundstoff enthält,

der Verbundstoff ein Produkt einer Reaktion zwischen der OD-Kohlenstoffnanostruktur, enthaltend eine erste reagierende Funktionsgruppe, und der 2D-Kohlenstoffnanostruktur, enthaltend eine zweite reagierende Funktionsgruppe, ist, und

die erste reagierende Funktionsgruppe und die zweite reagierende Funktionsgruppe jeweils unabhängig mindestens eines eines Halogenatoms, einer Hydroxylgruppe, einer Alkoxygruppe, einer Cyanogruppe, einer Aminogruppe, einer Azidgruppe, einer Carboxyamidingruppe, einer Hydrazinogruppe, einer Hydrazonogruppe, einer Carbamoylgruppe, einer Thiolgruppe, einer Estergruppe, einer Carboxylsäuregruppe oder eines Salzes davon, einer Sulfonsäuregruppe oder eines Salzes davon, und einer Phosphorsäuregruppe oder eines Salzes davon enthalten.

4. Hartmaskenzusammensetzung nach einem der Ansprüche 1 bis 3, wobei
die 0D-Kohlenstoffnanostruktur mindestens eines eines Fullerens, eines Bor-Buckyballs, eines Carborans und eines Derivats davon ist; und/oder
wobei die 2D-Kohlenstoffnanostruktur mindestens eines von Graphen, Graphenquantenpunkten, reduzierte, Graphenoxid und einem Heteroatomderivat davon ist; und/oder wobei eine Größe der 2D-Kohlenstoffnanostruktur in einem Bereich von 1 Nanometer (nm) bis 10 nm ist; und/oder
wobei ein Kohlenstoffgehalt in der 2D-Kohlenstoffnanostruktur in einem Bereich von 75 Gewichtsprozent (Gew.-%) bis 95 Gew.-% ist.

5. Hartmaskenzusammensetzung nach Anspruch 1, wobei
die 2D-Kohlenstoffnanostruktur ein Graphennanopartikel (GNP) mit einer Größe in einem Bereich von 1 nm bis 10 nm ist, und eine Anzahl von Schichten des GNP größer als 0 und kleiner oder gleich 300 ist; und/oder
wobei die 0D-Kohlenstoffnanostruktur ein Fulleren oder ein Derivat davon ist, und eine Anzahl von Kohlenstoffatomen in der 0D-Kohlenstoffnanostruktur eine von 60, 70, 76, 78, 82, 82 und 84 ist;
vorzugsweise wobei, gemäß einer Analyse des Fullerens durch Raman-Spektroskopie, eine maximale Absorptionsspitze bei einer Raman-Verschiebung von 1,455 Zentimeter^-1 (cm^-1) bis 1.500 cm^-1 beobachtet wird.

6. Hartmaskenzusammensetzung nach Anspruch 1, wobei
die 2D-Kohlenstoffnanostruktur ein 2D-Bogen mit einem Größen-zu-Dicken-Verhältnis in einem Bereich von 3 bis 30 ist.

7. Hartmaskenzusammensetzung nach Anspruch 1, wobei
die 2D Kohlenstoffnanostruktur ein GNP ist und

ein Intensitätsverhältnis einer D-Modusspitze zu einer G-Modusspitze, das aus einer Raman-Spektroskopieanalyse des GNP erlangt wird, größer als 0 und kleiner als oder gleich 2 ist, und ein Intenstitätsverhältnis einer 2D-Modusspitze zu einer G-Modusspitze 0,01 oder größer ist;

vorzugsweise wobei eine sp²-Kohlenstofffraktion des GNP gleich einer sp³-Kohlenstofffraktion davon oder gleich einem Vielfachen einer sp³-Kohlenstofffraktion davon ist.

8. Hartmaskenzusammensetzung nach einem der Ansprüche 1 bis 7, wobei
die 2D-Kohlenstoffnanostruktur mit der 0D-Kohlenstoffnanostruktur bei einem Verhältnis von 1:1 bis 99:1 gemischt ist.

9. Hartmaskenzusammensetzung nach Anspruch 1, wobei
die Hartmaskenzusammensetzung mindestens eines einer Verbindung, die durch Formel 2 repräsentiert wird, einer Verbindung, die durch Formel 3 repräsentiert wird, und eines Produkts einer Reaktion zwischen Graphen, an das eine Hydroxylgruppe gebunden ist, und einem Fulleren, an das eine Carboxylgruppe gebunden ist, umfasst:

wobei, in Formel 2, R eine durch Formel 2a repräsentierte Gruppe anzeigt:





wobei, in Formel 3, n eine ganze Zahl von 1 bis 10 ist.

10. Hartmaskenzusammensetzung nach einem der Ansprüche 1 bis 9, wobei das Lösungsmittel mindestens eines von Wasser, Methanol, Isopropanol, Ethanol, N,N-Dimethylformamid, N-Methylpyrrolidon, Dichlorethan, Dichlorbenzol, Dimethylsulfoxid, Xylen, Anilin, Propylenglykol, Propylenglykoldiacetat, 3-Methoxyl,2-propandiol, Diethylenglykol, Gamma-Butyrolacton, Acetylaceton, Cyclohexanon, Propylenglykolmonomethyletheracetat, o-Dichlorbenzol, Nitromethan, Tetrahydrofuran, Nitromethan, Dimethylsulfoxid, Nitrobenzol, Butylnitrit, Methylcellosolve, Ethylcellosolve, Diethylether, Diethylenglykolmethylether, Diethylenglykolethyl ether, Dipropylenglykolmethylether, Toluol, Hexan, Methylethylketon, Methylisobutylketon, Hydroxymethylcellulose und Heptan; und/oder
die Hartmaskenzusammmensetzung ferner umfasst:

eines eines ersten Materials, eines zweiten Materials und eines Gemischs des ersten Materials und des zweiten Materials, wobei

das erste Material eines eines Monomers, enthaltend einen aromatischen Ring, und eines Polymers, enthaltend eine das Monomer beinhaltende Wiederholungseinheit enthält, und

das zweite Material eines eines Hexagonalbornitrids, eines chalcogenidbasierten Materials und eines Vorläufers davon beinhaltet.

11. Verfahren zum Formen eines Musters, wobei das Verfahren umfasst:

ein Formen einer Ätzschicht auf einem Substrat,

ein Formen einer Hartmaske auf der Ätzschicht, wobei das Formen der Hartmaske ein Bereitstellen der Hartmaskenzusammensetzung nach einem der Ansprüche 1 bis 10 auf der Ätzschicht enthält, wobei die Hartmaske den Verbundstoff der 2D-Kohlenstoffnanostruktur und der 0D-Kohlenstoffnanostruktur enthält,

ein Formen einer Photoresistschicht auf der Hartmaske,

ein Formen eines Hartmaskenmusters, wobei das Formen des Hartmaskenmusters ein Ätzen des Verbundstoffs mithilfe der Photoresistschicht als Ätzmaske enthält; und

ein Ätzen der Ätzschicht mithilfe des Hartmaskenmusters als eine Ätzmaske; vorzugsweise ferner umfassend:

ein Ausführen einer Wärmebehandlung an der Hartmaskenzusammensetzung während oder nach dem Bereitstellen der Hartmaskenzusammensetzung auf der Ätzschicht.

12. Verfahren nach Anspruch 11, wobei eine Dicke der Hartmaske in einem Bereich von 10 nm bis 10.000 nm ist; und/oder
wobei das Formen der Hartmaske ein Verwenden mindestens eines von Rotationsbeschichtung, Luftsprühen, Elektrosprühen, Tauchbeschichten, Sprühbeschichten, Rakelbeschicthtung und Stabbeschichten während des Bereitstellens der Hartmaskenzusammensetzung enthält; und/oder
wobei das Formen der Hartmaske ein Mischen des Derivats der 2D-Kohlenstoffnanostruktur, des Derivats der 0D-Kohlenstoffnanostruktur und des Lösungsmittel enthält; und/oder
wobei das Derivat der 2D-Kohlenstoffnanostruktur mindestens eine eines COOHfunktionalisierten GNP und eines GNP-Vorläufers ist, und
das Derivat der 0D-Kohlenstoffnanostruktur ein OH-funktionalisiertes Fulleren ist; und/oder
wobei das Formen der Hartmaske
ein Mischen des Lösungsmittel und des die 2D-Kohlenstoffnanostruktur und der 0D-Kohlenstoffnanostruktur enthaltenden Verbundstoffs, oder
ein Mischen des Lösungsmittels, des Derivats der 2D-Kohlenstoffnanostruktur und des Derivats der 0D-Kohlenstoffnanostruktur enthält; oder wobei
das Formen des Hartmaskenmusters ein Formen einer Laminatstruktur enthält, und die Laminatstruktur die 2D-Kohlenstoffnanostruktur und die 0D-Kohlenstoffnanostruktur enthält.

13. Hartmaske, umfassend:

einen Verbundstoff, enthaltend eine 2D-Kohlenstoffnanostruktur und eine 0D-Kohlenstoffnanostruktur;

vorzugsweise wobei

die Hartmaske eine Laminatstruktur enthält, und

die Laminatstruktur die 2D-Kohlenstoffnanostruktur und die 0D-Kohlenstoffnanostruktur enthält.

14. Hartmaskenzusammensetzung, umfassend:

mindestens eins einer zweidimensionalen-(2D)-Kohlenstoffnanostruktur und eines Derivats der 2D- Kohlenstoffnanostruktur; und

mindestens eines einer nulldimensionalen-(OD)-Kohlenstoffnanostruktur und eines Derivats der 0D- Kohlenstoffnanostruktur.

15. Hartmaskenzusammensetzung nach Anspruch 14, wobei
die Hartmaskenzusammensetzung die 0D-Kohlenstoffnanostruktur enthält, und
die 0D-Kohlenstoffnanostruktur mindestens eines eines Fullerens, eines Bor-Buckyballs, eines Carborans und eines Derivats davon ist; oder wobei
die Hartmaskenzusammensetzung die 2D-Kohlenstoffnanostruktur enthält, und die 2D-Kohlenstoffnanostruktur mindestens eines eines Graphens, eines Graphennanopartikels (GNP), von Graphenquantenpunkten, eines reduzierten Graphenoxids und eines Heteroatomderivats davon enthält; oder
wobei
das mindestens eine der 2D-Kohlenstoffnanostruktur und des Derivats der 2D-Kohlenstoffnanostruktur die 2D-Kohlenstoffnanostruktur ist,
das mindestens eine der 0D-Kohlenstoffnanostruktur und des Derivats der 0D-Kohlenstoffnanostruktur die 0D-Kohlenstoffnanostruktur ist; und
die 2D-Kohlenstoffnanostruktur und die 0D-Kohlenstoffnanostruktur durch eine funktionelle Verknüpfergruppe miteinander verbunden sind.

Revendications

1. Composition de masque dur comprenant :

un solvant ; et

au moins l'un de

un mélange dérivé comportant un dérivé d'une nanostructure de carbone bidimensionnelle (2D) et un dérivé d'une nanostructure de carbone de dimension zéro (0D), ou

un composite comportant une nanostructure de carbone 2D et une nanostructure de carbone 0D.

2. Composition de masque dur selon la revendication 1,
ladite composition de masque dur comportant le composite,
ledit composite étant une structure dans laquelle la nanostructure de carbone 2D est liée à la nanostructure de carbone 0D par un lieur, ou
ledit composite étant un stratifié de la nanostructure de carbone 2D et de la nanostructure de carbone 0D ;
de préférence
ledit lieur étant au moins un groupe parmi un groupe ester (-C(=O)O-), un groupe éther (-O-), un groupe thioéther (-S-), un groupe carbonyle ((-C)=O)-), un groupe amide (-C(=O)NH-) et un groupe imide, ou
ledit lieur étant un groupe organique dérivé d'au moins un groupe parmi un groupe ester (-C(=O)O-), un groupe éther (-O-),un groupe thioéther (-S-), un groupe carbonyle ((-C)=O)-), un groupe amide (-C(=O)NH-) et un groupe imide.

3. Composition de masque dur selon la revendication 1,
ladite composition de masque dur comportant le composite,
ledit composite étant un produit d'une réaction entre la nanostructure de carbone 0D comportant un premier groupe fonctionnel réactif et la nanostructure de carbone 2D comportant un second groupe fonctionnel réactif, et
ledit premier groupe fonctionnel réactif et ledit second groupe fonctionnel réactif comportant chacun indépendamment un atome d'halogène, un groupe hydroxy, un groupe alcoxy, un groupe cyano, un groupe amino, un groupe azide, un groupe carboxamidine, un groupe hydrazino, un groupe hydrazono, un groupe carbamoyle, un groupe thiol, un groupe ester, un groupe acide carboxylique ou un sel de celui-ci, un groupe acide sulfonique ou un sel de celui-ci, et un groupe acide phosphorique ou un sel de celui-ci.

4. Composition de masque dur selon l'une quelconque des revendications 1 à 3,
ladite nanostructure de carbone 0D étant au moins une nanostructure parmi un fullerène, un buckminsterfullerène, un carborane et un dérivé de ceux-ci ; et/ou
ladite nanostructure de carbone 2D est au moins une nanostructure parmi le graphène, des points quantiques de graphène, l'oxyde de graphène réduit et un dérivé à hétéroatome de ceux-ci ; et/ou
la taille de la nanostructure de carbone 2D étant comprise dans la plage de 1 nanomètre (nm) à 10 nm ; et/ou
la teneur de carbone dans la nanostructure 2D étant comprise dans la plage de 75 pour cent en poids (75 % en poids) à 95 % en poids.

5. Composition de masque dur selon la revendication 1,
ladite nanostructure de carbone 2D étant une nanoparticule de graphène (GNP) ayant une taille comprise dans la plage de 1 nm à 10 nm et le nombre de couches de la GNP étant supérieur à 0 et inférieur ou égal à 300 ; et/ou
ladite nanostructure de carbone 0D étant un fullerène ou un dérivé de celui-ci et le nombre d'atomes de carbone dans la nanostructure de carbone 0D étant un nombre parmi 60, 70, 76, 78, 82, 82 et 84 ;
de préférence, conformément à l'analyse du fullerène par spectroscopie Raman, un pic d'absorption maximal étant observé à un décalage Raman de 1,455 centimètre^-1 (cm^-1) à 1500 cm^-1.

6. Composition de masque dur selon la revendication 1,
ladite nanostructure de carbone 2D étant une feuille 2D présentant un rapport taille sur épaisseur compris dans la plage de 3 à 30.

7. Composition de masque dur selon la revendication 1, ladite nanostructure de carbone 2D étant une GNP, et
le rapport d'intensité d'un pic de mode D sur un pic de mode G obtenu à partir d'une analyse par spectroscopie Raman de la GNP étant supérieur à 0 et inférieur ou égal à 2 et le rapport d'intensité d'un pic de mode 2D sur un pic de mode G est supérieur ou égal à 0,01 ;
de préférence la fraction de carbone sp² de la GNP étant égale à la fraction de carbone sp³ de celle-ci ou égale à un multiple de la fraction de carbone sp³ de celle-ci.

8. Composition de masque dur selon l'une quelconque des revendications 1 à 7,
ladite nanostructure de carbone 2D étant mélangée à la nanostructure de carbone 0D à un rapport de 1:1 à 99: 1.

9. Composition de masque dur selon la revendication 1,
ladite composition de masque dur comportant au moins l'un d'un composé représenté par la formule 2, d'un composé représenté par la formule 3 et d'un produit d'une réaction entre un graphène auquel un groupe hydroxy est lié et un fullerène auquel un groupe carboxy est lié :

dans laquelle, dans la formule 2, R indique un groupe représenté par la formule 2a :





dans laquelle, dans la formule 3, n représente un entier allant de 1 à 10.

10. Composition de masque dur selon l'une quelconque des revendications 1 à 9, ledit solvant étant au moins un solvant parmi l'eau, le méthanol, l'isopropanol, l'éthanol, le N,N-diméthylformamide, la N-méthylpyrrolidone, le dichloroéthane, le dichlorobenzène, le diméthylsulfoxyde, le xylène, l'aniline, le propylène glycol, le diacétate de propylène glycol, le 3-méthoxy-1,2-propanediol, le diéthylène glycol, la gamma-butyrolactone, l'acétylacétone, la cyclohexanone, l'acétate d'éther monométhylique de propylène glycol, le o-dichlorobenzène, le nitrométhane, le tétrahydrofurane, le nitrométhane, le diméthylsulfoxyde, le nitrobenzène, le nitrite de butyle, le méthyl cellosolve, l'éthyl cellosolve, le diéthyléther, l'éther méthylique de diéthylène glycol, l'éther éthylique de diéthylène glycol, l'éther méthylique de dipropylène glycol, le toluène, l'hexane, la méthyléthylcétone, la méthylisobutylcétone, l'hydroxyméthylcellulose et l'heptane ; et/ou
ladite composition de masque dur comprenant en outre :

l'un d'un premier matériau, d'un second matériau et d'un mélange du premier matériau et du second matériau,

ledit premier matériau comportant l'un d'un monomère contenant un noyau aromatique et d'un polymère comportant un motif récurrent contenant le monomère, et

ledit second matériau comportant un matériau parmi le nitrure de bore hexagonal, un matériau à base de chalcogénure et un précurseur de ceux-ci.

11. Procédé de formation d'un motif, le procédé comprenant :

la formation d'une couche de gravure sur un substrat,

la formation du masque dur sur la couche de gravure, la formation du masque dur comprenant la fourniture de la composition de masque dur selon l'une quelconque des revendications 1 à 10 sur la couche de gravure, ledit masque dur comportant le composite de la nanostructure de carbone 2D et de la nanostructure de carbone 0D ;

la formation d'une couche de photorésine sur le masque dur,

la formation d'un motif de masque dur, la formation du motif de masque dur comprenant la gravure du composite en utilisant la couche de photorésine comme masque de gravure, et

la gravure de la couche de gravure en utilisant le motif de masque dur comme masque de gravure ;

de préférence comprenant en outre :
la réalisation d'un traitement thermique sur la composition de masque dur pendant ou après la fourniture de la composition de masque dur sur la couche de gravure.

12. Procédé selon la revendication 11, l'épaisseur du masque dur étant comprise dans la plage de 10 nm à 10000 nm ; et/ou
la formation du masque dur comprenant l'utilisation d'au moins une technique parmi le revêtement par centrifugation, la pulvérisation d'air, l'électropulvérisation, le revêtement au trempé, le revêtement par pulvérisation, le revêtement à la racle et le revêtement par étalement pendant la fourniture de la composition de masque dur ; et/ou
ladite formation du masque dur comprenant le mélangeage du dérivé de la nanostructure de carbone 2D, du dérivé de la nanostructure de carbone 0D et du solvant ; et/ou
ledit dérivé de la nanostructure de carbone 2D étant au moins un dérivé parmi une GNP fonctionnalisée par COOH et un précurseur de GNP, et
ledit dérivé de la nanostructure de carbone 0D étant un fullerène fonctionnalisé par OH ; et/ou
ladite formation du motif de masque dur comprenant
le mélangeage du solvant et du composite comportant la nanostructure de carbone 2D et la nanostructure de carbone 0D, ou
le mélangeage du solvant, du dérivé de la nanostructure de carbone 2D et du dérivé de la nanostructure de carbone 0D ; ou
ladite formation du motif de masque dur comprenant la formation d'une structure stratifiée, et
ladite structure stratifiée comportant la nanostructure de carbone 2D et la nanostructure de carbone 0D.

13. Masque dur comprenant :

un composite comprenant une nanostructure de carbone 2D et une nanostructure de carbone 0D ;

de préférence

ledit masque comprenant une structure stratifiée et

ladite structure stratifiée comprenant la nanostructure de carbone 2D et la nanostructure de carbone 0D.

14. Composition de masque dur comprenant :

au moins l'un d'une nanostructure de carbone bidimensionnelle (2D) et d'un dérivé de la nanostructure de carbone 2D ; et

au moins l'un d'une nanostructure de carbone de dimension zéro (0D) et d'un dérivé de la nanostructure de carbone 0D.

15. Composition de masque dur selon la revendication 14,
ladite composition de masque dur comportant la nanostructure de carbone 0D et
ladite nanostructure de carbone 0D étant au moins une nanostructure parmi un fullerène, un buckminsterfullerène, un carborane et un dérivé de ceux-ci ; ou
ladite composition de masque dur comportant la nanostructure de carbone 2D et ladite nanostructure de carbone 2D étant au moins une nanostructure parmi le graphène, une nanoparticule de graphène (GNP), des points quantiques de graphène, l'oxyde de graphène réduit et un dérivé à hétéroatome de ceux-ci ; ou
ledit au moins l'un de la nanostructure de carbone bidimensionnelle (2D) et du dérivé de la nanostructure de carbone 2D étant la nanostructure de carbone 2D,
ledit au moins l'un de la nanostructure de carbone 0D et du dérivé de la nanostructure de carbone 0D étant la nanostructure de carbone 0D, et
ladite nanostructure de carbone 2D et ladite nanostructure de carbone 0D étant reliées l'une à l'autre par un groupe fonctionnel lieur.

Drawing